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  • Digitale Medien  (22)
  • 11
    Digitale Medien
    Digitale Medien
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Computational Chemistry 17 (1996), S. 1183-1196 
    ISSN: 0192-8651
    Schlagwort(e): Chemistry ; Theoretical, Physical and Computational Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Informatik
    Notizen: Ab initio molecular geometries and vibrational frequencies of various isolated vanadate species (VO3-4, HVO2-4, H2VO-4, and V2O4-7) were calculated using different pseudopotentials. The relative merits of these were assessed by comparing the calculated molecular parameters with the corresponding values obtained from calculations at all-electron levels and, whenever available, from X-ray studies for the salts. The calculations were extended to higher oligomers (V3O5-10, V4O6-13, and V4O4-12) using the pseudopotential whose basis functions are (10s5p5d)/[2s1p1d] (55/5/5) on vanadium and (4s4p)/[2s2p] (31/31) on oxygen, which yielded the best compromise between accuracy and computational effort. The results indicate a linear centrosymmetric geometry for the isolated V2O4-7 anion. The higher oligomers have less than 180° V(SINGLE BOND)O(SINGLE BOND)V angles, except the noncyclic tetraoligomer which has a linear central V(SINGLE BOND)O(SINGLE BOND)V angle (180°). The cyclic V4O4-12 species presents a planar structure with all the vanadium and bridging oxygen atoms in the same plane. This structure was alrea dy reported for the [(CH3)CNH3][V4O12] salt. The results suggest a lower stability of the linear V4O6-13 species, in agreement with previous reports. © 1996 by John Wiley & Sons, Inc.
    Zusätzliches Material: 4 Ill.
    Materialart: Digitale Medien
    Bibliothek Standort Signatur Band/Heft/Jahr Verfügbarkeit
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  • 12
    Digitale Medien
    Digitale Medien
    Chichester [u.a.] : Wiley-Blackwell
    Journal of Raman Spectroscopy 22 (1991), S. 519-523 
    ISSN: 0377-0486
    Schlagwort(e): Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: The Raman and infrared spectra of methyl trans-cinnamate were measured as a function of temperature in the liquid and solid phases. The temperature dependence of the band intensities established the presence of two conformers in the liquid phase (the s-cis and s-trans forms, with C=C—C=O dihedral angles equal to 0° and 180°, respectively; ΔH(s-trans)-(s-cis) = 3.43 ± 0.84 kJ mol-1) and led to the conclusion that the thermodynamically most stable s-cis form is the only form present in the solid.
    Zusätzliches Material: 4 Ill.
    Materialart: Digitale Medien
    Bibliothek Standort Signatur Band/Heft/Jahr Verfügbarkeit
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  • 13
    Digitale Medien
    Digitale Medien
    Chichester [u.a.] : Wiley-Blackwell
    Journal of Raman Spectroscopy 18 (1987), S. 115-118 
    ISSN: 0377-0486
    Schlagwort(e): Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: Raman spectra of di-n-butylamine show bands whose temperature-dependent intensities clearly suggest the occurrence of different conformers in simultaneous equilibria. In particular, the Raman spectrum of the solid phase is compared with that of n-nonane in order to identify the more stable conformation. In addition, intensity rations vs temperature for pairs of Raman bands in the CH stretching region exhibit a smooth variation between the liquid and solid.
    Zusätzliches Material: 3 Ill.
    Materialart: Digitale Medien
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  • 14
    Digitale Medien
    Digitale Medien
    Chichester [u.a.] : Wiley-Blackwell
    Journal of Raman Spectroscopy 25 (1994), S. 353-357 
    ISSN: 0377-0486
    Schlagwort(e): Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: Ab initio SCF MO calculations at the 3-21G level and the vibrational spectra [Raman and Fourier transform (FT) IR] of liquid-phase 2-chloro- and 3-chlorostyrene are reported. For 2-chlorostyrene, the ab initio calculations predict skew and gauche minima, with an energy difference of 11.5 kJ mol-1, and no evidence of more than one conformer was found in the liquid-phase Raman and FTIR spectra. The Raman spectra of liquid 3-chlorostyrene show pairs of bands whose temperature-dependent intensities clearly suggest the occurrence of a conformational equilibrium. From these bands, assigned to non-planar cis and trans conformers, a trans-cis energy difference of 2.3 ± 0.5 kJ mol-1 was obtained for the liquid phase.
    Zusätzliches Material: 4 Ill.
    Materialart: Digitale Medien
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  • 15
    Digitale Medien
    Digitale Medien
    Chichester [u.a.] : Wiley-Blackwell
    Journal of Raman Spectroscopy 25 (1994), S. 599-605 
    ISSN: 0377-0486
    Schlagwort(e): Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: Raman spectra of styrene (S), 3-fluorostyrene (3FS), 3-chlorostyrene (3CS) and 3-methylstyrene (3MS) and their complexes in α-, β- and γ-cyclodextrins (α-, β-, γCD) were recorded at various temperatures. The substituted styrene molecules were found to provide good group frequencies, namely, vC=C and vC—H, for probing the guest molecules. Generally, the C=C oscillator is shown to be a good probe for studying conformational equilibria of the guest molecule perturbed by complex formation with the various CD molecules. The CH oscillators provide information concerning plausible structures for the complexes. On the whole, all the spectral observations are consistent with different types of structures for the (S, 3MS)-αCD and (3FS, 3CS)-αCD complexes. In particular, the Raman spectroscopic results suggest that, for 3MS-αCD the vinyl group keeps some rotational freedom. For 3FS-αCD and 3CS-αCD, it is suggested that the most electronegative fluorine and chlorine atoms are left outside the the CD cavity, with the vinyl group rotationally hindered. For the γCD complexes, the wider CD cavity sould be able to accommodate all the guest molecules considered keeping the conformer distributions of the pure liquids approximately. However, the inclusion process seems to hinder the internal rotation in such a way that even below 200 K the conformer distribution remains similar to that of the pure liquid at room temperature.
    Zusätzliches Material: 7 Ill.
    Materialart: Digitale Medien
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  • 16
    Digitale Medien
    Digitale Medien
    Chichester [u.a.] : Wiley-Blackwell
    Journal of Raman Spectroscopy 18 (1987), S. 497-500 
    ISSN: 0377-0486
    Schlagwort(e): Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: A comparative Raman band shape study of the reorientation of monosubstituted benzene molecules (C6H5X, X = CH3, CH2Cl, CHCl2, CCl3 and C≡CCH3) in the liquid phase has been performed. Reorientational correlation functions appear to be less sensitive to molecular reorientation about the major axis (Z axis) than to rotation of the axis itself, approaching a symmetric top case. Molecular motion anisotropy is found to increase in the order C6H5CH3 〈 C6H5CH2Cl 〈 C6H5CHCl2 〈 C6H5CCl3 〈 C6H5CCCH3 as the rotation about the Z axis becomes increasingly preferred. These results are in agreement with NMR spin-lattice relaxation data.As expected for liquids with imporatant intermolecular interactions, both the free rotor and Kubo's model fail to fit the experimental correlation functions.
    Zusätzliches Material: 2 Ill.
    Materialart: Digitale Medien
    Bibliothek Standort Signatur Band/Heft/Jahr Verfügbarkeit
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  • 17
    ISSN: 0377-0486
    Schlagwort(e): Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: Raman spectra of ethylmethylamine and ethylmethylamine-N-d, both in the liquid phase, at different temperatures, and in the solid phase were recorded. Additionally, Fourier transform IR (4000 - 400 cm-1) spectra of these compounds in the liquid phase were also obtained. Normal coordinate calculations were performed for each conformer (T, G and G′), using an optimized local symmetry force field for secondary amines. These calculations allowed the assignment of the vibrational spectra, in good agreement with the experimental evidence. Whereas in the liquid phase all the three possible conformers were detected, in the solid phase only the bands ascribed to the T conformer were observed. From the temperature dependence study of the Raman spectrum of the liquid, the enthalpy differences between conformers were determined, yielding the values 4.6 ± 0.3 kJ mol-1 for ΔHG′-T′ 3.6 ± 0.3 kJ mol-1 for ΔHG - T and 1.1 ± 0.3 kJ mol-1 for ΔHG′- G. These were compared with ab initio SCF-MO results, for the isolated molecule, in order to assess the relative importance of intra-and intermolecular effects on conformational equilibria.
    Zusätzliches Material: 9 Ill.
    Materialart: Digitale Medien
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  • 18
    Digitale Medien
    Digitale Medien
    Chichester [u.a.] : Wiley-Blackwell
    Journal of Raman Spectroscopy 24 (1993), S. 699-703 
    ISSN: 0377-0486
    Schlagwort(e): Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: The Raman spectra of aqueous vanadium (V) solutions at different pH values, ranging from 13.1 to 7.0, are presented. The dominant bands in the range 700-1100 cm-1 are assigned to the VO symmetrical stretching of the different oligomers, using additional information from 51V NMR spectra and empirical models. The effects of pH, concentration and ionic strength on the oligomerization equilibria are discussed. The ionic strength is found to affect significantly the oligomer composition of vanadate solutions, which is of interest in biochemical and biological studies.
    Zusätzliches Material: 4 Ill.
    Materialart: Digitale Medien
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  • 19
    Digitale Medien
    Digitale Medien
    Chichester [u.a.] : Wiley-Blackwell
    Journal of Raman Spectroscopy 15 (1984), S. 224-231 
    ISSN: 0377-0486
    Schlagwort(e): Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: Evidence is provided concerning the internal rotation of the CHCl2 group in the C6H5CHCl2 molecule in the condensed phase using mainly the Raman spectra of the alkylic carbon-hydrogen stretching vibration of C6H5CHCl2 and its deuteriated analogues. Comparison of the Raman bands observed in the region of the CH stretching vibrations for the hydrogenated compound with its deuteriated derivatives allows the assingnment of two Raman bands to the C—H vibrator of the CHCl2 group. The dependence of the profiles of these bands on temperature and dilution in a series of solvents suggests a conformational equilibrium. Comparision of two different theoretical treatments of the isolated molecule enables us to reconize the importance of non-boarded interactions operating during the internal rotation of the dichloromethyl group. The experimental results, used together woth the theoretical studies, lead to the evidence for two probable rotational isomers, designated CH⊥ and CH‖ which are responsible for the two observed Raman bands.
    Zusätzliches Material: 14 Ill.
    Materialart: Digitale Medien
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  • 20
    Digitale Medien
    Digitale Medien
    Chichester [u.a.] : Wiley-Blackwell
    Journal of Raman Spectroscopy 26 (1995), S. 1033-1037 
    ISSN: 0377-0486
    Schlagwort(e): Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: The Raman spectra of liquid 3-methylstyrene show pairs of bands whose temperature-dependent intensities clearly suggest the occurrence of a conformational equilibrium. From these bands, assigned to cis and trans conformers, a trans-cis energy difference of 0.8 + 0.2 kJ mol-1 was obtained for the liquid phase. On the other hand, ab initio calculations at the 3-21G** and MP2/3-21G* levels predict a cis form more stable than the trans form by less than 0.15 kJ mol-1, in good agreement with gas-phase literature results.
    Zusätzliches Material: 3 Ill.
    Materialart: Digitale Medien
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