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  • 1990-1994  (420)
  • 1955-1959
  • 1990  (420)
  • Computational Chemistry and Molecular Modeling  (403)
  • somaclonal variation
  • transformation
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Years
  • 1990-1994  (420)
  • 1955-1959
Year
  • 1
    Electronic Resource
    Electronic Resource
    Springer
    Plant cell reports 9 (1990), S. 26-29 
    ISSN: 1432-203X
    Keywords: Solanum melongena ; eggplant ; Agrobacterium tumefaciens ; kanamycin ; transformation ; shoot regeneration
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Summary Kanamycin resistant plants of Solarium melongena L. (eggplant) cv. Picentia were obtained following the cocultivation of leaf explants with Agrobacterium tumefaciens. A disarmed binary vector system containing the neomycin phosphotransferase (NPTII) gene as the selectable marker and chloramphenicol acetyltransferase (CAT) as a reporter gene was utilized. In vitro grown plants were used as sources of explants to produce transgenic plants on selective medium containing 100 mg/l kanamycin. The transformation and expression of the foreign genes was confirmed by DNA hybridizations, leaf disc assays, and by measuring NPTII and CAT enzyme activities. This technique is simple, rapid, efficient, and transgenic eggplants of this commercial cultivar have been transferred to soil where they have flowered and set seed.
    Type of Medium: Electronic Resource
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  • 2
    ISSN: 1573-5028
    Keywords: direct gene transfer ; gene rearrangements ; Nicotiana tabacum ; particle gun ; transformation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract Transgenic tobacco plants and progeny carrying coding sequences for neomycin phosphotransferase II (NPTII) and beta-glucuronidase (GUS) were recovered following microprojectile bombardment of tobacco leaves. Transgenic plants were regenerated from bombarded leaf pieces of tobacco cvs. ‘Xanthi’ and ‘Ky 17’ which were cultured in the presence of 100 or 200 μg/ml kanamycin for six to eight weeks. Among 160 putative transgenic plants from at least 16 independent transformation events 76% expressed NPTII, and 50% expressed GUS. Southern analysis of plants expressing either one or both of the enzymes indicated DNA in high molecular weight DNA in 8 of 9 independent transformants analyzed. Two independent transformants and their progeny were analyzed in detail. Analysis of progeny for quantitative enzyme levels of NPTII and GUS, and Southern analysis of parents and progeny clearly demonstrated that the genes were transmitted to progeny. One transformant demonstrated Mendelian ratios for seed germination on kanamycin-containing medium while the other transformant had non-Mendelian ratios. DNA analysis of progeny indicate complex integration of the plasmid DNA, and suggest that rearrangements of this DNA has occurred. These results are consistent with other methods of direct DNA uptake into cells, and verify that the microprojectile bombardment method is capable of DNA delivery into intact plant cells which can give rise to transgenic plants and progeny.
    Type of Medium: Electronic Resource
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  • 3
    ISSN: 1573-5028
    Keywords: Agrobacterium ; conifers ; DNA hybridization ; transformation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract The hypervirulent Agrobacterium tumefaciens strain A281 formed frequent tumors (31%) on Picea abies (Norway spruce), an economically important tree species in Swedish forests. Three-month-old seedlings were inoculated and tumors were established that grew hormone-independently in culture. Tumors contained agropine and mannopine/mannopinic acid as determined by acid pH paper electrophoresis. In addition, DNA hybridization studies showed that the DNA from these tumor lines contained sequences homologous to Ti plasmid T-DNA, whereas wild-type spruce seedling DNA did not. These results suggest that Agrobacterium vectors can be used for gene transfer into this important forest species.
    Type of Medium: Electronic Resource
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  • 4
    ISSN: 1573-5028
    Keywords: cytokinin ; tumor formation ; isopentenyltransferase gene ; Nicotiana ; genetic tumors ; polymerase chain reaction (PCR) ; transformation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract The shooty morphology of a nontumorous amphidiploid mutant of Nicotiana glauca Grah. x N. langsdorffii Weinm. was restored by cytokinins, whether exogenously applied or endogenously produced by transformation of the mutant with a transfer DNA (T-DNA) cytokinin-biosynthesis gene (isopentenyltransferase; ipt). Auxins alone did not confer this effect. Similar transformation was not achieved for the parental species. In the case of transformation with the ipt gene, selection of the transformed tissues was based on its hormone-independent growth in the presence of the antibiotic kanamycin. Transformed tissues exhibited a shooty morphology, indistinguishable from that of wildtype genetic tumors N. glauca x N. langsdorffii. This altered phenotype was caused by the presence and constitutive expression of the ipt gene. The insertion and expression of this gene in transformed tissues was confirmed by using the polymerase chain reaction (PCR) technique as well as conventional molecular hybridization analysis. Expression of the ipt gene led to an elevated level of cytokinin in the transformed mutant tissues. This evidence supports the notion that genetic tumors are caused, at least in part, by elevated levels of cytokinin in interspecific hybrids.
    Type of Medium: Electronic Resource
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  • 5
    ISSN: 1573-5028
    Keywords: Agrobacterium rhizogenes ; Agrobacterium tumefaciens ; root induction ; tzs ; Linum usitatissimum L. ; transformation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract Root induction on flax (Linum usitatissimum L.) cotyledon explants by Agrobacterium rhizogenes strain 1855 is markedly increased by co-inoculation with disarmed A. tumefaciens strain LBA 4404 containing a plasmid carrying the tzs gene of pTiC58. Most of the roots (estimated to be more than 90%) were transformed. This effect is most likely due to the secretion of trans-zeatin by A. tumefaciens stimulating the division of plant cells making them more receptive to transformation by A. rhizogenes, although other explanations are possible. This observation supports the idea that the tzs gene, although not essential for transformation, may promote transformation. An obvious application for genetic engineering experiments involving transformation by A. rhizogenes, is to include a vir-induced tzs gene in the transformation system to help maximize transformation efficiency.
    Type of Medium: Electronic Resource
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  • 6
    ISSN: 1573-5028
    Keywords: antisense ; gene expression ; plants ; regulation ; RNA ; transformation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract We have shown leaf-specific inhibition GUS gene expression in transgenic Nicotiana plants using an antisense RNA with a 41-base homology spanning the translation start codon of the gene. GUS was expressed from the nominally constitutive 35S promoter and the antisense RNA was expressed from the light-regulated ca/b promoter of Arabidopsis thaliana. A range of GUS inhibition from 0 to 100% was obtained by screening a small population of transgenic plants and the specific levels of inhibition observed were stably inherited in two generations. An antiGUS ‘gene’ dosage effect was observed in plants which were homozygous for antiGUS. RNA detection results suggest that duplex formation with the 41 base pair antiGUS RNA destabilized the GUS mRNA and that an excess of antisense. RNA was not required. Our results demonstrate the potential of antisense RNA as a strategy for obtaining plant mutants, especially ‘down mutations’ in essential genes where only a short 5′ sequence of the mRNA is required. They also suggest that the ‘position effect’ on gene expression could be used in conjunction with an antisense RNA strategy to provide a versatile approach for crop improvement.
    Type of Medium: Electronic Resource
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  • 7
    Electronic Resource
    Electronic Resource
    Springer
    Plant molecular biology 14 (1990), S. 815-824 
    ISSN: 1573-5028
    Keywords: Agrobacterium tumefaciens ; hypocotyls ; Nicotiana alata ; regeneration ; self-incompatibility ; transformation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract A transformation and regeneration system has been developed for Nicotiana alata, a plant which is being intensively studied as a model of gametophytic self-incompatibility. Plantlets can be regenerated efficiently from seedling hypocotyls. Kanamycin-resistant, transformed plants have been obtained by cocultivation of regenerating hypocotyls with Agrobacterium tumefaciens strain LBA4404 containing a binary vector. The transformation frequency was low with 〈1% of tissue explants regenerating transformed plants. The transformed plants contained from one to three copies of the introduced DNA. In most cases, the kanamycin resistance phenotype was transmitted to the offspring as a normal Mendelian factor. In one unusual case, none of the offspring inherited the kanamycin resistance of the transformed maternal parent. This plant may have been chimeric or the kanamycin resistance gene may have been inactivated.
    Type of Medium: Electronic Resource
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  • 8
    Electronic Resource
    Electronic Resource
    Springer
    Cancer and metastasis reviews 9 (1990), S. 93-98 
    ISSN: 1573-7233
    Keywords: transformation ; progression ; autotrophs
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract In 1984, Philippe Shubik wrote in an editorial in the Journal of the National Cancer Institute [1] that: ‘In terms of general biology, the multicellular organisms have evolved a complex series of defensive responses to extracellular injury involving various inflammatory reactions and their systemic concomitants. Needless to say, these reactions are by no means always successful from the standpoint of the host and indeed may well be the immediate cause of the obvious ill effects noted. The unicellular organisms, in contrast, react to injury by dividing and moving. In the search for the features that may link chemical, physical, and viral carcinogens apart from their ability to induce neoplasia, only one characteristic in common is obvious, namely, their ability to produce intracellular change or injury while leaving the cell viable. Perhaps the initial and fundamental characteristic of neoplasia is a reversion of the cell to unicellular behavior. Division and invasiveness are the characteristics of the neoplastic cell, and increased motility certainly seems to be the most likely mechanism for invasion’. Dr. Shubik presented these views as a basis for ‘further discussion’ regarding the nature of the neoplastic response. We hope that this presentation will augment Shubik's plea by reviewing his idea in the context of our current knowledge of tumor development. In addition, we will attempt to integrate the concept of the unicellular behavior of tumor cells with Foulds' [2] and subsequently Nowell's [3] insightful hypothesis concerning tumor progression.
    Type of Medium: Electronic Resource
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  • 9
    Electronic Resource
    Electronic Resource
    Springer
    Plant foods for human nutrition 40 (1990), S. 283-288 
    ISSN: 1573-9104
    Keywords: heat ; transformation ; fatty acids ; leaf proteins
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract Freeze-dried leaf protein concentrate (LPC) contained 18% lipids in which linolenic acid (61.5%) was the major component. Linolenic acid in LPC was almost stable when stored at ambient temperature (30 to 35°C) and exposed to air for 24 weeks. Heating of LPC (50 to 200°C) in presence of moisture (6 to 12%) progressively increased the rate of destruction of linolenic acid. Below 100°C the presence of lipids did not affect the protein quality but at higher temperatures due to the lipid oxidation protein quality as estimated by dye-binding capacity was considerably affected.
    Type of Medium: Electronic Resource
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  • 10
    Electronic Resource
    Electronic Resource
    Springer
    Euphytica 51 (1990), S. 249-256 
    ISSN: 1573-5060
    Keywords: Festuca arundinacea ; tall fescue ; chromosome pairing ; electrophoresis ; isoenzyme ; meiotic analyses ; somaclonal variation ; tissue culture
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Summary This study was conducted using the isozymes ACP-1, ADH-1, GOT-2, GOT-3, MDH, 6-PGD-1 and PGI-2 to: a) compare isozyme banding patterns of tall fescue somaclones with parents and b) correlate tissue culture-induced chromosome abnormalities with variant banding patterns. The 174 somaclones were grouped into seven categories based on their meiotic analyses and time of regeneration from culture. Differences in isozyme frequency between categories compared by chi-square tests were greatest for MDH, 6-PGD-1 and PGI-2, and least for ACP-1. The most significant differences in frequency were found between somaclones and parents. In comparisons of somaclone categories, the most different isozyme distributions were between the early vs. late regenerated somaclones. No significant differences in isozyme frequencies were found between all 42-chromosome somaclones vs. aneuploid somaclones and the three somaclone groups (42-normal, 42-abnormal, aneuploid) compared to each other. This study suggests that culture-induced isozyme variation alters the distribution of the isozyme phenotypes, but is not directly correlated with chromosome abnormalities.
    Type of Medium: Electronic Resource
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  • 11
    Electronic Resource
    Electronic Resource
    Springer
    Euphytica 46 (1990), S. 35-41 
    ISSN: 1573-5060
    Keywords: forage legumes ; Lotus corniculatus ; birdsfoot trefoil ; somaclonal variation ; tissue culture
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Summary Seventy-two plants regenerated from leaf-derived calli of a single plant of Lotus corniculatus have been evaluated for several morphological and agronomical traits. The analysis of selfed and polycross progenies of the regenerants indicates that the variation among regenerants was, at least in part, of genetic origin. Most of the mutations induced by tissue culture were recessive and were detected only after sexual propagation. Although in vitro culture had a depressive effect for most of the traits, the selfed progenies of 2 regenerants displayed higher values for leaflet width and seed yield than the selfed progeny of the initial plant. However the somaclonal variation did not increase the variation for any trait with respect to the variation of the donor cultivar of the initial plant.
    Type of Medium: Electronic Resource
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  • 12
    ISSN: 1573-5060
    Keywords: Brassica juncea ; Indian mustard ; in vitro selection ; salt-tolerance ; somaclonal variation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Summary In vitro selection of salt tolerant plants of Brassica juncea L. (Indian mustard) cv. Prakash has been accomplished by screening highly morphogenic cotyledon explant cultures on high NaCl media. Out of a total of 2,620 cotyledons cultured on high salt medium, 3 survived, showed sustained growth and regenerated shoots. They were multiplied by axillary bud culture on NaCl free medium. The salt-selected shoots retained salt tolerance following 3 month of growth and multiplication on control medium. While two of these somaclones flowered and set seeds, third one grew slowly, had abnormal leaf morphology and was sterile. The seed of the two fertile plants were sown in the field to raise R1 segregating generation. Data were recorded for field, other agronomic components and oil content. The somaclonal lines, both selected salt-tolerant and non-selected, showed tremendous amount of variation for all the characters studied. One of the two tolerant somaclones invariably showed reduced height, longer reproductive phase and higher 1000 seed weight. Based on the agronomic performance of R1 plants of these somaclones, some plants were selected and their progeny were evaluated for agronomic performance under standard field conditions and salt-tolerance in the greenhouse using sand pot culture method. Most of the lines bred true for their specific characteristics. In the greenhouse, selected salt-tolerant somaclones (SR-2 and SR-3) performed better for plant growth, yield and other agronomic traits at higher salt treatments, indicating thereby that salt-tolerance trait selected in vitro was expressed in the whole plants and is genetically stable and transmitted onto the progeny. The two tolerant lines, however, differed in their salt-tolerance during vegetative and reproductive phases as indicated by their salt-tolerance and stress susceptibility indices. The mechanism of salt-tolerance is not clear and needs to be further investigated.
    Type of Medium: Electronic Resource
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  • 13
    Electronic Resource
    Electronic Resource
    Springer
    Plant cell, tissue and organ culture 23 (1990), S. 39-44 
    ISSN: 1573-5044
    Keywords: albino ; aspen ; chimera ; callus culture ; somaclonal variation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract Pigment as well as isozyme variations were observed among aspen (Populus tremuloides Michx.) plants regenerated from callus cultures. Out of more than 600 plantlets, two chimeric plants (one with green base and two albino shoots and the other with an albino shoot) were produced. Callus derived from albino shoots produced albino as well as chimeric plants when transferred to shoot inducing medium. Isozyme patterns of 119 plants were examined by starch gel electrophoresis. Thirty plants showed variation in shikimic dehydrogenase isozyme and 41 in isocitric dehydrogenase. Variation was also observed in malate dehydrogenase and phosphoglucose isomerase. No variation was seen in 6-phosphogluconate dehydrogenase. Pigment variation was not associated with any isozyme changes.
    Type of Medium: Electronic Resource
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  • 14
    ISSN: 1572-994X
    Keywords: HPV 16 ; transformation ; NIH 3T3 cells ; polycistronic mRNA ; cDNA cloning ; sequencing
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract We have cloned cDNA of the major 1.8 kb mRNA from HPV 16-transformed NIH 3T3 cells (PM3T3). The entire nucleotide sequences of this cDNA were determined and compared with prototype HPV 16 genomic DNA sequences. The 5′-end of the cDNA was flanked by approximately 300 bp of cellular sequences, and the 3′-end of the cDNA sequences contained poly A residues following at nt 4230. HPV 16 sequences began at nt 124, downstream of a major viral p97 promoter, within the E6 open reading frame (ORF). The first splice donor site was at nt 226 and the splice acceptor site was at nt 409, suggesting that the E6 gene is inert. Second splice donor and acceptor sites were located at nt 880 and at nt 3357, respectively. This mRNA was thus shown to consist of three exons, resulting in polycistronic mRNA containing three potentially functional virus early genes-E7, E1^E4, and E5-actively transcribed in the transformant.
    Type of Medium: Electronic Resource
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  • 15
    Electronic Resource
    Electronic Resource
    Springer
    Plant cell, tissue and organ culture 22 (1990), S. 135-145 
    ISSN: 1573-5044
    Keywords: co-transformation ; liposomes ; tobacco ; transformation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract A system for the transformation of tobacco mesophyll protoplasts using pH-sensitive liposomes was developed. Plasmid DNA (plGVneo23) encoding the NPT-II gene for kanamycin resistance was entrapped in pH-sensitive liposomes composed of dioleolphosphatidylethanolamine, cholesterol and oleic acid. These liposomes release their contents at low pH and are capable of delivering their contents into the cytoplasm of protoplasts. Kanamycin-resistant colonies were reproducibly recovered from transformed protoplasts at an average frequency of 1.62×10-4 at pH 7.5. Plants regenerated from transformed cell lines were normal in appearance and were fertile. NPT-II activity was detected in leaf extracts of transformed, kanamycin-resistant plants and the presence of NPT-II DNA in the tobacco genome was shown by Southern blots. Analysis of self-pollinations and reciprocal crosses to non-transformed plants indicated that kanamycin resistance segregated as a dominant nuclear marker. Co-transformation of protoplasts with liposomes containing two selectable markers indicated that co-transformation occurred with a frequency of approximately 23%.
    Type of Medium: Electronic Resource
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  • 16
    ISSN: 1573-6822
    Keywords: Transforming growth factor β1 ; cell cycle ; liver ; epithelial cell line ; transformation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: The effects of TGFβ1 on cell cycle events in a rat liver derived epithelial cell line (BL9) and in two in vitro transformants of this line were studied by flow cytometry. Using either ethidium bromide staining or the incorporation of bromodeoxyuridine to evaluate DNA synthesis it was shown that TGFβ1 prevented the entry of G0/G1 phase BL9 cells into S phase. TGFβ1 did not exert its inhibitory effect(s) on DNA synthesis by the modulation of early events in the cell cycle. The tumorigenic transformed BL9 cell lines gave contrasting responses to the effects of TGFβ1. DNA synthesis in a BL9 cell line derived by transfection with an active N-ras oncogene was unaffected by TFGβ1 and thus appeared refractory to its growth controlling effects. On the other hand cells from a BL9 cell line derived by in vitro transformation with activated aflatoxin B1 retained their sensitivity to the effects of TGFβ1. Thus the loss of the inhibitory effect of TGFβ1 on DNA synthesis is not obligatory for the malignant transformation of rat liver epithelial cells.
    Type of Medium: Electronic Resource
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  • 17
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 37 (1990), S. 15-34 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In this paper a multireference constant denominator perturbation theory (CDPT) is developed to reduce incomplete basis set errors arising when solving the Schrödinger equation with a finite basis set. The advantage of this method is that very few basis functions are needed, and all calculations if carried out to high enough order in the perturbation treatment effectively use a complete basis set. As a first step the theory has been restricted to one-particle Hamiltonians and applied to the anharmonic oscillator to study the convergence properties. For perturbation calculations carried out to fifth order, results from Pade approximates show an improvement in accuracy of between one and three orders of magnitude.
    Additional Material: 4 Tab.
    Type of Medium: Electronic Resource
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  • 18
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 37 (1990), S. 155-165 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The physical context of the high ionic conductivity of the H+ and OH- ions in aqueous solutions is considered. Quantum dynamical aspects of the mobility of these ions are investigated, especially within the framework of the complex scaling method (CSM). It is argued that the high ionic mobilities under consideration are due to quantum delocalization of the ions as well as mass interference of the H+ ions with water protons. This effect is formally described with the aid of the coherent-dissipative structures, which become spontaneously created in the solution owing to the thermal motion. In particular, (1) a novel connection between the proton transfer rate (as measured by NMR) and the mobilities of the considered ions (as determined by conductivity measurements) is derived. Additionally, (2) a relation connecting the activation energies of the above reaction rates with the ionic mobilities is found. The above relations contain no fitting parameters. Comparisons with experimental results is made, which also reveals the predictive power of the present CSM treatment in the field of microdynamical processes in condensed phases.
    Additional Material: 1 Ill.
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  • 19
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 37 (1990), S. 207-207 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 20
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 37 (1990), S. 655-662 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The aim of this article is to give a practical way for the use of real spherical functions in another frame than the frame in which they have been defined. For instance, we calculate physical properties from a local frame and use them in the general frame, deduced one from the other by Eulerian rotations on the coordinates. The power of the method is in the use of cartesian coordinates and in the definition of a scalar product between these functions to set up the complete vectorial space generated by these representations of the group O3+.
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  • 21
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 37 (1990), S. 309-310 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 22
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 37 (1990), S. 313-313 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 23
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 37 (1990), S. 389-402 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Hubbard theory is an approximation to the Pariser-Parr-Pople theory which presents many of its important features in a relatively simple form. Our Hubbard Hamiltonian employs a single electron-correlation parameter: 0 ≤ x ≡ U/(t + U) ≤ 1, where t is the one-electron hopping integral (the negative of the Hueckel β), and U is the Hubbard one-center, two-electron repulsion parameter. This parameter provides the Hubbard connection between the following: (1)Molecular orbital and valence bond theory(2)The exchange approximation and full CI(3)Conductors and insulators(4)Fermi-Dirac and Boltzmann statistics(5)Normal and superconductorsWe present Hubbard theory in the freeon (spin-free) formulation where each N-electron state is pictorially represented by a Gel'fand diagram which specifies both the orbital configuration and the multiplicity. The simplicity of the freeon formulation makes the Hubbard connection quite transparent.
    Additional Material: 7 Ill.
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  • 24
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 37 (1990), S. 437-448 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We have examined variations in bond orders in conjugated hydrocarbons that follow improvement in MO calculations on going from topological Hückel MO to self-consistent Pariser-Parr-Pople-type calculations. Differences in individual bond orders can be interpreted as pointing to increased weights of selected Kekulé valence structures. Significantly, so indicated valence structures are those with the largest number of formal Kekulé benzene rings or the largest contribution to molecular resonance energy in terms of conjugated circuits.
    Additional Material: 4 Ill.
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  • 25
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 37 (1990), S. 497-508 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Parametrized computational procedures and simplified physical models of molecular reality are often related to one another but are by no means the same thing. With special reference to work by Koutecky and by Cizek, Paldus et al., it is shown here that the PPP model rests on a simple but physically sound electrostatic picture of a molecular π system, and its intrinsic difference from an independent particle model is emphasized. As an illustration of the heuristic power which makes physical models powerful tools of theoretical research, ground state charge transfer GSCT, in situ molecular electronegativity, and the principle of electronegativity equalization are derived within the PPP-CI scheme, no use being made of molecular orbitals, and the assumptions on which the CT theory rests are made explicit.
    Type of Medium: Electronic Resource
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  • 26
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The electronic structure of C60 cages are examined by use of the INDO and INDO/CI methods. The calculated spectrum of Buckminsterfullerene has one allowed low-lying band at 27,300 cm-1, to be compared with an experimental value of 25,900 cm-1. These calculations suggest that other cage structures are not stable, or they are not ground state singlets.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
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  • 27
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 37 (1990), S. 663-677 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: An extension of the IPPP (inner projections of the polarization propagator) method to theoretically analyze transmission mechanisms of indirect nuclear spin-spin couplings is presented. The localization technique used is modified so that all the canonical molecular orbitals of a compound may be localized to represent chemical bonds, lone pairs, and the corresponding antibonding molecular orbitals. These localized molecular orbitals, together with the polarization propagator, are used to obtain an intuitive picture of how a coupling is generated as a sum of terms, each one consisting of two particle-hole single excitations. This picture can be used to identify underlying transmission mechanisms and quantitatively evaluate their importance toward the total coupling. The paramagnetic spin-orbit and the spin-dipole interactions are studied in detail.
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  • 28
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    International Journal of Quantum Chemistry 37 (1990), S. 701-711 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A computational scheme based on a “mixed basis set” approach is applied to the study of the structure and the energetics in proton transfer systems. Five hydrogen-bonded systems of the type (CH3HnA ‥ H ‥ BHmCH3)+, where A and B can be N, O, or S, have been investigated with various minimal and extended basis sets. Calculations with the extended basis set yield double-well potential energy curves, which the minimal basis set is unable to reproduce. Calculations with the mixed basis set, constructed from an extended basis set on the atoms engaged in the hydrogen transfer part and a minimal basis set on the rest of the molecule, give predictions of geometries, potential energy curves, and relative energies similar to the results from the extended basis set. Inclusion of polarization functions in the mixed basis set becomes essential in systems that contain third row atoms. This scheme should become useful in studies of large molecules in which different parts can be represented at different levels of computational complexity.
    Additional Material: 3 Ill.
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  • 29
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    International Journal of Quantum Chemistry 37 (1990), S. 773-783 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: This paper explains a method for finding saddle points on a multidimensional surface and shows how it may be used to define saddle-point seeking curves that have properties similar to well-known orthogonal trajectories. It is shown that a gradient extremal is a special case of one of these curves, and its chemical significance as the path, defined by local criteria, which starts from a stable structure and leads to a transition state, is discussed briefly in relation to the intrinsic reaction coordinate. It is emphasized that this theory gives a natural method for locating points that have Hessians of similar structure to those of transition states.
    Additional Material: 3 Ill.
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  • 30
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    International Journal of Quantum Chemistry 37 (1990), S. 753-771 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Explicit equations for the constants a and b of the energy as the average expectation value for the minimal domain of states giving the Roothaan energy functional are derived in terms of the total spin value and the “seniority” quantum number. The state with off-diagonal long-range order can appear in the framework of the Roothaan scheme for the quasidegenerate system as an alternative to the Hund rule. Admissible many-electron states are established for all configurations of the icosahedral symmetry group systems, and corresponding a and b coefficients are calculated.
    Additional Material: 3 Tab.
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  • 31
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    International Journal of Quantum Chemistry 37 (1990), S. 811-819 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The correlation potential is computed for two electron atomic ions with atomic numbers from 1 to 10 using the charge density reconstructed from a natural orbital expansion of a Kinoshita-like atomic wave function. Over the wide range of densities involved, the correlation potentials are not even approximately a local function of the density.
    Additional Material: 4 Ill.
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  • 32
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    International Journal of Quantum Chemistry 38 (1990), S. 41-53 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In this paper, the symmetrized basis function method is extended and used for the classification of the total spin states of many-electron systems. The reduction matrix, which is expressed as a series of products and direct products of matrices is derived. It is very advantageous that the method can be completed by computer. As an example, the reduction matrix for a 5-electron system calculated by IBM PC computer and the classification of the total spin states is presented.
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  • 33
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    International Journal of Quantum Chemistry 38 (1990), S. 75-83 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In this paper, the TST-CEQ calculated results including the reactive cross sections and rate constants for the Cl + HCl reaction at the specified vibrational state of the HCl are presented. It is shown that the oscillatory behavior of the system in the three-dimensional world does not appear, and the larger the vibrational quantum number of HCl, the smaller the cross sections ¯QTST-CEQ (E, ν) are at a given total energy used in the calculations, but the larger the reactive rate, constants KTST-CEQ (T, ν) are at a given temperature. The KTST-CEQ (T, v) is the same as when first published, and the average reactive rate constants KTST-CEQ (T) are close to the ones by Garrett and Schatz et al.
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  • 34
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    International Journal of Quantum Chemistry 38 (1990) 
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    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 35
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    International Journal of Quantum Chemistry 38 (1990), S. 383-388 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A formalism is suggested of the so-called local symmetricized orbitals to be used for the construction of a symmetricized basis in molecular electronic structure calculations. The local symmetricized orbitals are defined as additive contributions to the symmetry orbitals of a molecule that arise from symmetry operations of a corresponding atom. The local symmetricized orbitals are transformed according to the irreducible representations of the molecular symmetry group. This approach appears to be most suitable for the optimization of quantum mechanical calculations accounting for the spatial symmetry of compounds under consideration. This fact is due to the formalism of the local symmetricized orbitals that explicitly accounts for the local symmetry of basis function centers, which is essential for such optimization.
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  • 36
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    International Journal of Quantum Chemistry 38 (1990), S. 173-179 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: This short review concerns the protonation of Schiff bases by halogenic or carboxylic acids with a bias toward the chromophore of visual and bacterial rhodopsins. It is pointed out that the weak acids available in these pigments could not protonate the retinyl Schiff base 100% and that a supporting mechanism is needed to achieve full protonation. Our Fourier transform infrared studies both at room and low temperatures relating to this problem are summarized, and the propable role of water is emphasized.
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  • 37
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    International Journal of Quantum Chemistry 38 (1990), S. 215-219 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The application of the MBPT in the localized representation requires that both the occupied and the virtual orbitals obtained by the canonical HF equation should be localized. The localization of the occupied orbitals is straightforward in general by any localization method. It is shown that by using Boys' method the localized virtual orbitals are spatially well separated and transferable not only in minimal basis sets.
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  • 38
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    International Journal of Quantum Chemistry 38 (1990), S. 231-238 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Cis-trans photoisomerization of ethylene, some of its methyl and fluoro derivatives, methaniminium, and aminoborane was studied and twisted biradical geometries of these molecules in So, S1, and S2 states were optimized using the half-electron version of the MNDO method with configuration interaction. The results are quite satisfactory, in good agreement with available ab initio data.
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  • 39
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    International Journal of Quantum Chemistry 38 (1990), S. 279-282 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: New possibilities of the spin-extended Hartree-Fock method in determining the sequence of energy levels are analyzed and demonstrated by the example of some oxygen-contained compounds.
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  • 40
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    International Journal of Quantum Chemistry 38 (1990), S. 395-417 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The one-electron density matrix (DM) of crystalline systems is discussed, especially concerning its longrange behavior; reference is made throughout to systems treated at a Hartree-Fock-LCAO-SCF level of approximation. The analysis is performed on the assumption of generally smooth behavior of eigenvalues and eigenvectors in k (reciprocal) space, so that they can be expressed by means of a truncated Fourier expansion. This assumption allows us to obtain analytic approximations for the DM, on the basis of the information collected at a few, suitably selected sampling k points. It is therefore possible at the same time to discuss the influence of structural parameters (dimensionality of the system, existence and shape of the Fermi surface, structure of the chemical bonds) and to set up a computational scheme that is general and simple enough.
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  • 41
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    International Journal of Quantum Chemistry 38 (1990), S. 461-486 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: This study is a unified approach to quantum theories of polyacen carcinogenesis. Part I discusses the M, L, and B regions theory. Although the M region of polyacens is much less reactive than is the K region, the chemical reactivity of these two regions parallels each other. Consequently, the K-L Pullman's theory may be reformulated by replacing the K region by the M region. The M-L regions theory improves all the quantum structure-carcinogenic activity relationships obtained previously in the K-L framework. Moreover, it would appear that in these correlations, the most important role is played by nonconcerted electrophilic reactions. We suggest that the M-L modified Pullman's theory and the Bay (B) region theory, proposed by Jerina et al., are related to different steps of the metabolic activation mechanism leading to ultimate carcinogen: the first step for the Pullman's theory and the carbocation step for the theory of the Bay region. We have termed the “M, L and B regions theory” as this unified approach to the problem of polyacens carcinogenesis.
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  • 42
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    International Journal of Quantum Chemistry 38 (1990) 
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    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 43
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    International Journal of Quantum Chemistry 38 (1990), S. 501-520 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The role, and limitations, of the fundamental physical quantities used in our current system of dosimetry for the protection of individuals against the hazardous effects of ionizing radiation is discussed briefly. A major limitation is the inability to correlate biological data, in a unified way, as a function of linear energy transfer with the consequent necessity for quality factors.From consideration of the various interaction processes undergone by charged particles in the equilibrium slowing down spectra generated by the incident radiation field, it is shown that good correlation of biological effects, for all radiation types, can be achieved in terms of linear primary ionization. The implication is that delta-ray effects play at most a very minor role, at moderate fluences, and that, consequently, the absorbed dose is an unsuitable parameter for describing radiation effects. Structure in the radiosensitive targets is observed to have a critical dimension of about 2 nm. It occurs only when double-stranded DNA is present and the magnitude of the inactivation probability is consistent with double-stranded breaks being the significant lesion. Calculation is made of the yield of lesions as a function of the mean free path for primary ionization.Differential spectra of radiation quality are obtained for monoenergetic electrons (0.2 keV to 30 MeV); for characteristic X-rays from carbon, aluminium, neon, potassium, copper, silver, and tungsten; for 50 kV X-rays, 250 kV X-rays, 241Am, 137Cs, and 60Co gamma rays; and for neutrons with energies between 0.1 and 50 MeV. Damage by electrons is shown to be predominant at the ends of their tracks between 50 and 200 eV, whereas this is not so for the proton recoil spectrum generated by neutrons above 1 MeV.Proposals are made for a unified system of dosimetry that is independent of radiation type and that obviates the need for quality factors. The method is thought to be of general applicability to irradiations by nuclides incorporated into mammalian cells, by ingested emitters, and by external sources.
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  • 44
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    International Journal of Quantum Chemistry 38 (1990), S. 597-605 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: By a way of partitioning of Mulliken overlap populations, the hybrid orbitals of central atoms and ligands are obtained by the CNDO method. The dipole moments of some hybrids are calculated using the hybrid orbitals obtained, and they are mostly in accordance with experimental values. In addition, overlap integrals may be decomposed into components, and then σ, π, and δ hybrid orbitals can be obtained.
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  • 45
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    International Journal of Quantum Chemistry 38 (1990), S. 611-611 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 46
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    International Journal of Quantum Chemistry 38 (1990), S. 653-664 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Five energy hypersurfaces of the most examined pericyclic reactions have been investigated by using ab initio SCF, CASSCF, and the semiempirical AM1 methods. The systems are H4, H6, C3H6, C4H4, and C3OH4. Stationary points and their sets of harmonic vibrational frequencies have been calculated by means of analytical gradient techniques in the frameworks of the respective approaches. ZPE corrected energy barriers are based on single-point calculations including dynamical correlation corrections by CAS-CI(SD)+DC, CASCEPA, or MP2.
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  • 47
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    International Journal of Quantum Chemistry 38 (1990) 
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    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 48
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    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In order to understand the interaction mode of benzodiazepine ligands with their peripheral binding sites, the structural and electronic properties of a benzodiazepine Ro 5-4864, Alpidem, PK 11195, and some analogs are characterized at the ab initio molecular orbital level. Conformational and electronic data, with a particular emphasis on electrostatic aspects, i.e., molecular electrostatic potentials, Mulliken atomic charges, and potential-derived charges, are used as input within molecular superimpositions to elaborate the pharmacophoric elements for the peripheral benzodiazepine ligands. A putative three-dimensional (3-D) steric and electronic model is proposed.
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  • 49
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    International Journal of Quantum Chemistry 38 (1990), S. 27-34 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The molecular transform is an alternate means of considering numerical representations of molecules in a manner designed to generate indices that can be related to structural and physiochemical parameters. The literature has shown that the transform, actually the Fourier transform, is operable on representations such as Cartesian coordinates or graphically derived depictious reflected by adjacency or distance matrices. The resulting curve may be used to give a binary index of the molecule or integrated to give an area-related index; either of these indices may be used as a correlation parameter in structure-activity studies. In this instance the individual bond distance matrices of a series of structurally diverse compounds served as input for a transform program. The derived index was then used to correlate both physical property and pharmacological activity indices for the series; correlation coefficients were comparable to those reported for the valence molecular connectivity parameter of Kier and Hall. The study also showed that lower correlation coefficients resulted when the index was based on the transform of hydrogen-suppressed structures.
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  • 50
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    International Journal of Quantum Chemistry 38 (1990), S. 263-276 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: An algorithm for locating stationary points corresponding to local minima and transition states on potential energy surfaces is further analyzed. This method utilizes local gradient and Hessian (i.e., first and second energy derivative) information to generate a series of “steps” that are followed to the desired stationary point. By designing the step sequence to move energetically downhill in all coordinates, local minima can be found. By stepping uphill along one local eigenmode of the Hessian while minimizing the energy along all other modes, one locates transition states. Key elements of this development are more efficient parameterization of the step vector in terms of quantities that permit the direction (i.e., uphill or downhill), and length of the step to be carefully controlled, and implementation of the ability to explore “side channels” as attractive options occur.
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  • 51
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    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The HeI photoelectron (PE) spectra of No,No-dimethyl-monothiooxamide (1,) its analogue Ns,Ns-dimethylmonothiooxamide (2), dithiooxamide (3), N,N′-dimethyldithiooxamide (4), and N,N,N′,N′-tetramethyldithiooxamide (5) are presented. The results of CNDO/2 calculations, the PE spectra of the related compounds acetamide, thioacetamide, thiourea, and their methyl derivatives, and HeI/HeII intensity considerations are used to assign the spectra.
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  • 52
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    International Journal of Quantum Chemistry 38 (1990), S. 851-857 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We describe our implementation of geometry optimization techniques within the linear combination of Gaussian-type orbitals (LCGTO) approach to local-density functional theory. The algorithm for geometry optimization is based on the evaluation of the gradient of the total energy with respect to internal coordinates within the local-density functional scheme. We present optimization results for a range of small molecules which serve as test cases for our approach.
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  • 53
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    International Journal of Quantum Chemistry 38 (1990), S. 881-889 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 1 Ill.
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    International Journal of Quantum Chemistry 38 (1990), S. 893-893 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 55
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    International Journal of Quantum Chemistry 38 (1990), S. 531-547 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We review the nature of the problem in the framework of Rayleigh-Schrödinger perturbation theory (the polarization approximation) considering explicitly two examples: the interaction of two hydrogen atoms and the interaction of Li with H. We show, in agreement with the work of Claverie and of Morgan and Simon, that the LiH problem is dramatically different from the H2 problem. In particular, the physical states of LiH are higher in energy than an infinite number of discrete, unphysical states and they are buried in a continuum of unbound, unphysical states, which starts well below the lowest physical state. Claverie has shown that the perturbation expansion, under these circumstances, is likely to converge to an unphysical state of lower energy than the physical ground state, if it converges at all. We review, also, the application of two classes of exchange perturbation theory to LiH and larger systems. We show that the spectra of three Eisenschitz-London (EL) class, exchange perturbation theories have no continuum of unphysical states overlaying the physical states and no discrete, unphysical states below the lowest physical state. In contrast, the spectra of two Hirschfelder-Silbey class theories differ hardly at all from that found with the polarization approximation. Not one of the EL class of perturbation theories, however, eliminates all of the discrete unphysical states. The best one establishes a one-to-one correspondence between the lowest energy states of the unperturbed and perturbed Hamiltonians, and a one-to-two correspondence for the higher states. We suggest that the EL class perturbation theories would be good starting points for the development of more effective perturbation theories for intermolecular interactions.
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  • 56
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    International Journal of Quantum Chemistry 38 (1990), S. 585-591 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Electron propagator calculations of Sc and Ti ionization energies employing contractions based on atomic natural orbitals reveal the soundness of this approach for choosing basis sets. Errors in total energies greatly exceed those for ionization energies, where contraction errors are reduced to less than 1 mhartree. Systematic improvements involve retention of natural orbitals with lower occupation numbers and augmentation with diffuse and polarization functions.
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  • 57
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    International Journal of Quantum Chemistry 38 (1990), S. 633-644 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Computation is carried out by the motion of the state of a dynamical system. This description unites digital and “neural network” computation. The use of an energy function to understand and to program batch mode computation on feedback networks is reviewed. Recognizing words in continuous speech illustrates the use of a compound network to solve a real-world problem where data arrive continuously over time. A new tool, a Lagrangian formulation, is introduced for studying networks which oscillate, and as a means for formulating problems which need to optimize functional integrals.
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  • 58
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    International Journal of Quantum Chemistry 38 (1990), S. 681-682 
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    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 59
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    International Journal of Quantum Chemistry 38 (1990), S. 717-719 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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    International Journal of Quantum Chemistry 38 (1990), S. 701-706 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Floating spherical Gaussian basis sets are systematically expanded for a series of small molecules: methane, ammonia, ethane, and acetylene. Localized (nonorthogonal) molecular orbitals are each constructed as a linear combination of up to five functions of the form exp [- (r - R)2/ρ2], where the size ρ and the position R of each function is optimized according to the variation principle. Basis sets are obtained for the C and N cores, the C —; H and N — H bonds, the N lone pair, and the C — C and C—C bonds. Only three to five fully optimized functions are required to describe the main features of each bond orbital, including the negative lobes in the wavefunctions at the heavy atoms and the local maximum in the electron density at the hydrogen atoms. The energies obtained with three basis functions for the core orbitals are intermediate between the results of RHF-SCF calculations with STO-3G and 3-21G basis sets.
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  • 61
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    International Journal of Quantum Chemistry 38 (1990), S. 753-765 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We provide a numerical test of a new approach to calculating approximate interatomic interaction energies based on partial antisymmetry (PA) [Adams, Chem. Phys. Lett. 68, 511 (1979)]. We use spin-coupled products of single determinant atomic wave functions to approximate a particular primitive wave function of the diatomic. Three methods are used: (1) the conventional full antisymmetry (FA) approach, in which the primitive wave function is antisymmetrized and the difference of expectation values of the total energies of the diatomic and atomic systems is calculated, (2) the PA approach, in which only some of the terms of the antisymmetrizer are applied to the primitive wave function, and the energy expressions are simplified based on approximations to the PA theorem [Adams, op. cit.], and (3) a hybrid approach based on a combination of assumptions from the first two approaches, which is comparable to the work of Dacre and McWeeny [Proc. Roy. Soc. London A317, 435 (1970)]. Results are compared with accurate potential curves from the literature. Interaction energies were calculated for the X 1Σ+g states of Ne2, Li2, and Na2, the X 1Σ+ states of LiNa and LiF, the x 3Σ+u states of Li2 and Na2, x 7Σ+u, and x 3Σ+ LiNa at several internuclear distances. In all cases but Ne2, the PA and FA interaction energies are much closer to each other than is either to the accurate reference values. In these cases there is thus no significant penalty exacted for the use of PA over FA, even though it is easier to use. By conventional reasoning, neither the PA nor the Dacre-McWeeny approaches should work at short range or for binding molecules, because they truncate expansions of the antisymmetrizer in the energy expression. Our results provide counter examples to change that expectation, thus providing additional evidence in support of an approximate approach based on the PA theorem.
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  • 62
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    International Journal of Quantum Chemistry 38 (1990), S. 821-833 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: When a molecular solute is immersed in a polar and polarizable solvent, the electronic wave function of the solute system is altered compared to its vacuum value; the solute electronic structure is thus solvent-dependent. Further, the wave function will be altered depending upon whether the polarization of the solvent is or is not in equilibrium with the solute charge distribution. More precisely, while the solvent electronic polarization should be in equilibrium with the solute electronic wave function, the much more sluggish solvent orientational polarization need not be. We call this last situation “non-equilibrium solvation.” We outline a nonlinear Schrödinger equation approach to these issues. The nonlinearity arises from the self-consistent aspect that the solute electronic Hamiltonian depends on the solvent electronic polarization which is induced by the solute charge distribution. We illustrate the predictions of the theory for electron transfer reactions, ionic dissociations, and solvation dynamics in polar solvents. Special features of interest include activation barriers that differ markedly from standard predictions, and novel solvent dynamical features.
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  • 63
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    International Journal of Quantum Chemistry 38 (1990), S. 843-850 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Previous energy-based criteria for aromaticity developed from one electron eigenvalues (using methods ranging from Huckel to ab initio calculations) have not correlated well with experimentally derived criteria such as χ⊥nlcl or chemical reactivity data, and are particularly poor for heteroaromatic compounds. Previous work has shown that criteria derived from the lowest π molecular orbitals of heteroaromatic compounds correlate well with χ⊥nlcl and chemical reactivity, prompting us to modify Kollmar's procedure for determining aromatic stabilization energies by localizing the lowest π orbital rather than the entire π bonding manifold. This modified procedure was implemented with both the natural (NLMO) and Boys orbital localization methods, and was applied to a set of ten five-membered ring heteroaromatics and to pyridine and its diazine derivatives. The new criterion ΔπL correlated well with χ⊥nlcl (R2 = 0.86 (NLMO); R2 = 0.92 (Boys)) for five-membered rings, and with theoretical measures of aromaticity for both sets of heteroaromatics. The Boys procedure gave better overall correlations and was markedly superior for pyrazole and pyridazine.
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  • 64
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    International Journal of Quantum Chemistry 38 (1990), S. 115-117 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 65
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    International Journal of Quantum Chemistry 38 (1990), S. 149-161 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The influence of the geometry on the specifics of the electronic structure of Li6 clusters is studied in detail, since planar and three-dimensional lithium hexamers are found to be of comparable stability. The ab initio CI investigation of the Li6 isomers yields almost degenerate lowest singlet and triplet states for certain cluster geometries. Simple criteria for the energy gap between the lowest triplet and singlet state are derived, and their applicability is demonstrated.
    Additional Material: 5 Ill.
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  • 66
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    International Journal of Quantum Chemistry 38 (1990), S. 321-327 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The method of quasi-classical trajectories on an LEPS hypersurface was used for studying the influence of the exchange of one or both of the hydrogen atoms for deuterium in the reaction H1 + H2Br. As expected, the reaction cross sections of the exchange and abstraction reactions were found to increase if H1 was replaced by D and decrease if H2 was replaced by deuterium. A similar change in the reaction cross sections have also been observed for vibrationally excited reactants. The distribution of vibrational (rotational) energy is related to the ωe (Be) values of the respective reactants and products.
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  • 67
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    International Journal of Quantum Chemistry 38 (1990), S. 339-350 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A three-dimensional potential energy surface for the 2A′ ground state of the system (Ne—H2)+ (2Σ+ in collinear geometry) has been calculated at SCF and CEPA levels. This surface describes the abstraction reaction \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm Ne} + {\rm H}^ + _2 \to {\rm NeH}^{\rm + } + {\rm H}, $$\end{document} which is endoergic by 0.57 eV (ΔH00) and has been studied recently by different experimental groups at low collision energies. Our CEPA calculations yield an endoergicity of 0.55 eV (ΔH00). The 2A′ surface has a minimum at collinear geometry with RNe - H = 2.29 a0 and RH—H = 2.08 a0 and a well depth of 0.49 eV relative to Ne + H+2. The effects of electron correlation on the shape of the surface and on the well depth are discussed.An analytic fit of the collinear part of the surface has been constructed based on Simon's proposal of using polynomials in the coordinates (R—Re)/R instead of (R—Re). The fitted potential is used for quantum mechanical scattering calculations with the finite element method (FEM). Preliminary results for reaction probabilities for H+2 in different vibrationally excited states are given and compared to the experimental results.
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  • 68
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    International Journal of Quantum Chemistry 38 (1990), S. 389-394 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A suggested formalism of the local symmetricized orbitals in conjunction with the selection technique for independent blocks of integrals in an original basis is used for a construction of multielectron Hamiltonian matrix elements in the symmetry orbital basis. The optimal molecular electronic structure calculation algorithm with the Hartree-Fock-Roothaan method in the symmetricized basis was obtained as a result. The minimal number of fundamentally distinguished (symmetry attributed) elements both in original and in symmetricized basis is used in the calculations.
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    International Journal of Quantum Chemistry 37 (1990), S. 205-205 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 70
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    International Journal of Quantum Chemistry 37 (1990) 
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    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 71
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    International Journal of Quantum Chemistry 37 (1990), S. 249-256 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The present paper is aimed at differentiability of electronic wave functions, with respect to parametric variables, in the presence of electronic degeneracy. An analysis is made of a wave function, constructed so that it has the largest domain of parameter space in which it is differentiable, with the help of Berry's formula for the geometric phase. In particular, the electronic wave functions, in presence of a double degeneracy in two- and three-dimensional parameter spaces, are studied in detail. It was found that the three-parameter-dependent wave function is differentiable everywhere except along an axis starting from the degenerate point where it is discontinuous. The two-parameter-dependent wave function is differentiable everywhere except at the degenerate point where it is disocontinuous. These singularities are expected to have consequences on wave functions having parametric variables as arguments.
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  • 72
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    International Journal of Quantum Chemistry 37 (1990), S. 271-289 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We have carried out an ab initio STO-5G computational analysis of the electrostatic potentials of four structural analogues of the highly toxic 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) and four related aromatic systems benzo[a]pyrene, benz[a]anthracene, and two isomeric benzoflavones. These systems, to varying degrees, induce aryl hydrocarbon hydroxylase activity and are believed to interact with the same cytosolic receptor in initiating their biochemical responses. Our present results for the TCDD analogues support and have allowed us to further qualify our early observations regarding factors which are linked to high biological activities in the dibenzo-p-dioxins and structurally similar systems. We find that a high degree of activity appears to require nonoverlapping negative potentials above all or most of the lateral regions, with an observed optimum range of magnitudes. In systems with central oxygens, it is required that the negative oxygen potentials be small and weak; however, oxygen negative regions in the molecule are not necessary for high activity. The observed differences between the potential patterns of the four aromatic systems and those of TCDD and its active analogues may reflect an inherent dissimilarity in the nature of their interactions with the cytosolic receptor. That the carbonyl oxygen negative potential of 7,8-benzoflavone is significantly more negative than its isomer's supports earlier speculation concerning the former's more effective inhibiting effects on metabolic oxidation.
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  • 73
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    International Journal of Quantum Chemistry 37 (1990), S. 167-196 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The electronic structures of undoped and doped copper oxides and other related oxides are investigated on the basis of the N-band Hubbard models. The Hubbard Hamiltonians for clusters of transition metal oxides are exactly diagonalized by the full valence-bond (VB) configuration interaction (CI) method in order to elucidate populations of doped holes, electronic excitation energies, etc. Possible mechanisms of the high-Tc superconductivity for oxide superconductors are discussed on the basis of the calculated results, together with available experiments. The analysis of correlation and spin correlation effects on doped copper oxides indicates theoretical possibilities of new models for organic and organometallic magnetic conductors and superconductors. Organic and organometallic analogs to copper oxides are therefore proposed on the basis of these results.
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  • 74
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    International Journal of Quantum Chemistry 37 (1990), S. 221-240 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Oscillator strengths for transitions involving levels of three spectral series, 3s2 1S → 3snp1P0, 3s3p 1P0 → 3snd 1D, and 3s3p 1P0 → 3sns 1S, have been computed and analyzed for several ions of the MgI isoelectronic sequence (MgI-TiXI). The quantum defect orbital (QDO) formalism has been used throughout, and the results are comparable to those of more complex theoretical procedures.
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  • 75
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    International Journal of Quantum Chemistry 37 (1990) 
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    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 76
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    International Journal of Quantum Chemistry 37 (1990), S. 747-752 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A method is presented for obtaining rapidly convergent upper and lower bounds to the eigenvalues of the Schrödinger equation for one-dimensional and central-field models. The logarithmic derivative of the wave function is written as a Padé approximant and the bounds are obtained by simply counting the real zeroes of the denominator.
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  • 77
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    International Journal of Quantum Chemistry 37 (1990), S. 317-317 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 78
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    International Journal of Quantum Chemistry 37 (1990), S. 349-371 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: An historical account is given of the part played by the author in the development of PPP theory in the early 1950s.
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  • 79
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    International Journal of Quantum Chemistry 37 (1990), S. 415-422 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The idea of interpreting the semiempirical MO theories from a constrained variational point of view is explored. A density-based approach is developed for calibrating the parameters of useful semiempirical Hamiltonians of molecular electronic structure theory. Results of some numerical experiments with model Hamiltonians of constrained variational origin are reported.
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  • 80
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    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Based on the completely optimized S0, S1, and S2 molecular geometries of azulene, the vibronic structure of the S1 ← S0 absorption as well as of the S1 → S0, S2 → S1, and S2 → S0 fluorescences is investigated theoretically within the adiabatic approximation. By means of theory-experiment comparisons, the influence of non-Condon terms and of the Dushinsky effect on the vibronic structure of azulene spectral behavior is discussed. Typical for the S1 ← S0 absorption and the S1 → S0 fluorescence are vibronic transition moment contributions of Condon type, whereas the interpretation of azulene S2 → S1 and S2 → S0 fluorescences is successful only within the scope of the Herzberg-Teller approach by taking into account vibronic coupling terms and, additionally, the Dushinsky effect in the latter case. An analysis of the relevant vibrational modes is given.
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  • 81
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    International Journal of Quantum Chemistry 38 (1990) 
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    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 82
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    International Journal of Quantum Chemistry 38 (1990), S. 99-114 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 83
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    International Journal of Quantum Chemistry 38 (1990), S. 129-138 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The polymerization mechanism of tetramethylenes was reinvestigated under inclusion of solvent effects. The approach of a methanol molecule to a borderline diradical, a typical diradical, and a typical zwitterion was studied by a valence, charge, and dipole moment analysis of SINDO1 calculations. Whereas the solvent molecule has no effect on the character of the zwitterion, the borderline diradical was found to switch to a zwitterion at the approach of the methanol molecule if the distance between the donor carbon and the methanol oxygen is below 2 Å. A similar switch of character was observed for the typical diradical at CO distances below 1.5 Å. From energy considerations it is concluded that borderline diradicals can follow a zwitterionic polymerization mechanism in polar solvents, whereas typical diradicals are much less likely to do so.
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  • 84
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    International Journal of Quantum Chemistry 38 (1990), S. 163-171 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We describe a package of some IBM PC programs that may find application in computer-aided molecular design. PCGEOM constructs and visualizes molecular models from bond lengths, bond angles, and dihedral angles, from Cartesian coordinates, or from stored fragments. It may prepare output files to be used as input for other programs, like CNDOB (conventional CNDO/2) or PCMEP using the bond increment (BI) method for the calculation of molecular electrostatic potentials. PCPROT is in preparation and will use Protein Data Bank coordinates to visualize and manipulate protein molecular models. Starting from these, it will calculate electrostatic potentials using the BI method and/or monopoles adjusted to reproduce ab initio values for amino acid residues. FSCF is based on a CNDO-type approximation and uses strictly localized molecular orbitals in order to partition large molecules into a central fragment, a polarizable region, and a fully transferable environment. The partition allows one to handle relatively large systems with up to 200 atoms. To illustrate applications, we present estimation of relative inhibitory potencies of a series of substituted triazines on chicken liver dihydrofolate reductase.
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    International Journal of Quantum Chemistry 38 (1990), S. 209-213 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The possible role of the nonlinear coupling on the character of the dynamics of particle transfer process is investigated. The analysis and solutions of the kinetic equation indicate that nonlinear coupling causes symmetry breaking of particle transfer potential and determines possible equilibrium structure of the system. Dissipative coupling characterizes the rate of the system to reach thermodynamic equilibrium and along with nonlinear coupling and parameters of the system determines in a unique way the resulting equilibrium structure of the system.
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    International Journal of Quantum Chemistry 38 (1990), S. 239-244 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A local electronic-state density in β-cristobalite in the empirical tight-binding approximation has been calculated by the recursion method. In particular, silicon clusters have been considered in β-cristobalite containing up to three coordination spheres of silicon atoms.
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  • 87
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    International Journal of Quantum Chemistry 38 (1990), S. 297-309 
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    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A new form of the generalized master equation for electronic excitation transfer in a partially disordered polymer chain was derived. Within this equation, in order to differentiate the transfer in ordered parts of the partially disordered polymer chain, we decomposed the memory function of electronic excitation into several parts. These parts are memory functions associated with various types of subdynamics of electronic excitation. The partially disordered polymer chain where the disorder is caused by conformational defects is discussed.
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  • 88
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    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Extended Hückel band calculations, frontier crystal orbital analysis, and degenerate-level perturbation theory are used to evaluate the effect inclusion of bulk-layer interactions has on the relative stabilities of ordered overlayers. Five patterns of hydrogen atoms chemisorbed on unreconstructed graphite (11% coverage) are examined for the Bernal (ABABAB…) and registered (AAA…) three-dimensional stackings. The single-layer two-dimensional approximation for graphite is found not to be entirely satisfactory for the type of chemisorption pattern stability questions addressed in this paper.
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  • 89
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    International Journal of Quantum Chemistry 38 (1990), S. 867-867 
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    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 90
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    International Journal of Quantum Chemistry 38 (1990), S. 623-640 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A new formalism has been developed in order to evaluate intermolecular interaction energies for organometallic complexes including electrostatic, polarization, and orbital contributions based on extended Hückel molecular orbital (EHMO) theory. The electrostatic interaction is evaluated using (i) a multipolar expansion of EHMO charge density, or (ii) by calculating directly the electrostatic integrals in the basis of atomic orbitals. The polarization effects are evaluated by introducing a perturbation into the Hamiltonian. The orbital interaction is calculated by considering a supermolecule made of the organometallic substrate and a model electrophile or nucleophile. To provide the shortest possible response time on an interactive computer graphics facility, this model should require the minimum amount of computer time, which explains why approximate procedures are used to evaluate the dominant contributions to the interaction energies. Preliminary results show that these interaction energies lead to reaction potentials in good agreement with experiment for a broad series of nucleophilic and electrophilic addition or substitution reactions involving organometallic complexes. In addition, it is shown that the method can easily be extended for the calculation of solvent effects. To this end, developments considering the supermolecule surrounded by a polarizable continuum are in progress.
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    International Journal of Quantum Chemistry 38 (1990), S. 419-433 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The one-electron density matrix (DM) of a number of crystalline systems - lithium, graphite, boron nitride, silicon, and beryllium - are considered here, as resulting from Hartree-Fock-SCF-LCAO calculations. The influence of structural and computational parameters is discussed. It is shown in particular why the structure of chemical bonds in semiconductors leads to an oscillating long-range behavior of the DM, similar to that observed in metals, where these oscillations are related to the very existence of a Fermi surface. Concerning computational parameters, the influence of the density of sampling k points and of basis set on the calculated DM is considered; it is shown that the choice of the basis set is not a very critical one as far as the DM range is concerned. Some critical aspects of the interrelation between DM range and exchange part of the Fock Hamiltonian are analyzed.
    Additional Material: 12 Ill.
    Type of Medium: Electronic Resource
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  • 92
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 38 (1990), S. 497-497 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 93
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 38 (1990), S. 521-531 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Semiempirical computations were carried out to determine the tunneling rates in the case of coupled motion of two protons along the reaction coordinate. The following molecular systems were studied for medium intermolecular distances (A - B = 2.72 or 2.75 Å); +AH - BH - A, where A was NH3 or H2O and BH was HF or H2O. In the cases where the bridge was HF, solvation was modeled with just one water molecule attached to each side of the perpendicular axis through HF at 2.75 Å. Coupled motion of three protons was also included in the case of H3O - H2O - H2O - H2O.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
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  • 94
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 38 (1990), S. 559-572 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A generating function approach based on molecular orbital graph theory is presented that provides a straightforward way of obtaining the secular polynomials and energy bands for repeated unit systems from polynomial recurrence expressions. The possibility of obtaining the analytical energy-level spectrum of the system can also be predicted. These results are then used to discuss the vibrational problems of finite chain systems with single- and double-component lattices. It seems to be the first report describing the vibrational states of an (AB)N chain.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
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  • 95
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 38 (1990), S. 608-608 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 96
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 38 (1990), S. 613-613 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 97
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Compact representation of molecular charge distribution in molecular crystals has been derived from ab-initio crystal orbital wavefunction within the framework of cumulative atomic multipole moment (CAMM) expansion. Results for HF, CO2, and cubane C8H8 crystals have been compared with values calculated for corresponding clusters within conventional LCAO MO SCF approach. CAMM technique has also been used to represent molecular charge distribution in electronic excited states using CI wavefunction obtained from multireference configuration interaction (MRD-CI) calculations. This approach supplements previously introduced uncorrelated and correlated CAMM's and allows accurate nonempirical modeling of electrostatic effects involving molecules in excited states or in crystalline environment. Improved point charge model derived from CAMM has been also described.
    Additional Material: 6 Tab.
    Type of Medium: Electronic Resource
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  • 98
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Using hydrogen-like wave functions, a two-parameter and a four-parameter variational density-functional calculation of the total atomic binding energy of Ne atom is carried out. The total-energy values, together with values obtained for the electron (number) density at the nucleus, are compared with a previous three-parameter variational density-functional calculation and with single-zeta Hartree-Fock values.
    Additional Material: 3 Tab.
    Type of Medium: Electronic Resource
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  • 99
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 38 (1990), S. 167-185 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A new computational technique is presented to calculate approximate reaction paths in complex molecules. The method is based on the Gaussian chain approach proposed by Elber and Karplus [1] but avoids some computational difficulties of this technique. It is also more than 10 times faster. The new formulation is quite general and enables empirical interpolation between two types of motions which differ considerably: trapped and ballistic (see also “Note Added in Proof”). We present test results for two model molecules: alanine dipeptide (AD) and isobutyryl-(ala)3-NH-methyl (IAN). The optimization of the chain is very stable and provides an approximate continuous path even if the initial guess is poor.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
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  • 100
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 38 (1990), S. 245-249 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Molecular dynamics simulations of pure water are reported. Ewald summation is found to retard translational diffusion. Results are compared for several simulations using different boundary conditions.
    Additional Material: 2 Tab.
    Type of Medium: Electronic Resource
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