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  • 1
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    Journal of Mathematical Physics 26 (1985), S. 1626-1639 
    ISSN: 1089-7658
    Source: AIP Digital Archive
    Topics: Mathematics , Physics
    Notes: The splitting theorem, previously derived for symmetric operators, is generalized to arbitrary one- and two-particle operators. The notion of alternant systems, as defined in various semiempirical theories of alternant hydrocarbons, is accordingly generalized to arbitrary Hamiltonians. A simple test to decide whether or not a given Hamiltonian is alternant is obtained. A configuration interaction space Xn generated by n electrons moving over 2n orthonormalized orbitals is considered. Eigenstates Ψ ∈ Xn of alternant Hamiltonians are contained in complementary spaces X+n and X−n, subspaces of the space Xn. Each state Ψ± ∈ X±n is called alternantlike, and it has characteristic properties of eigenstates associated with neutral alternant hydrocarbons, such as uniform charge density distribution, vanishing bond orders between vertices of the same parity, etc. The complete set of linear properties associated with one- and two-particle operators and common to all alternantlike states Ψ± ∈ X±n is obtained.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 101 (1994), S. 5281-5292 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: First, a new approach to treat the strongly correlated conjugated-circuit model on two-dimensional networks is made with computational effort comparable to that for corresponding tight-binding models. Toward this end a translationally symmetric arrow assignment is used to construct an antisymmetrically signed "adjacency'' matrix for two-dimensional networks. Then symmetry blocking is used to manipulate this "adjacency'' matrix, and make the associated conjugated-circuit computations. Second, a series of two-dimensional translationally symmetric structures related to graphite is constructed by means of a kind of local rearrangement on the graphite lattice. A consequent detailed description of π-electron resonance energy via conjugated-circuit computations is presented for these novel two-dimensional nets as well as several other regular and semiregular nets with vertices of degree 3. Approximate energy estimates indicate that resonance stability depends dominantly on the local topology of the networks, and in particular on the fraction of faces which are hexagonal.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    s.l. : American Chemical Society
    Analytical chemistry 48 (1976), S. 1405-1412 
    ISSN: 1520-6882
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 4
    Electronic Resource
    Electronic Resource
    Springer
    Theoretical chemistry accounts 61 (1982), S. 363-368 
    ISSN: 1432-2234
    Keywords: Heats of atomization ; Conjugated hydrocarbons ; Semiempirical method
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Heats of atomization of a range of conjugated hydrocarbons are calculated by a semiempirical method which combines characteristic features of the MO and the VB theory. The π-ground state of each hydrocarbon is represented as a linear combination of Kekulé structures where, unlike the VB theory, each Kekulé structure is a determinant containing bond Orbitals. In this approach only the Hückel parameter has to be adjusted. Experimental heats of atomization are by this method reproduced approximately equally well as by the more sophisticated SCF-MO approach. The use of this method is however much simpler since it amounts to a single diagonalization of a matrix of the order equal to the number of Kekulé structures only.
    Type of Medium: Electronic Resource
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  • 5
    ISSN: 1432-2234
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 6
    Electronic Resource
    Electronic Resource
    Springer
    Theoretical chemistry accounts 73 (1988), S. 207-219 
    ISSN: 1432-2234
    Keywords: Alternant hydrocarbons ; Bond orders ; Bond orbital resonance theory (BORT)
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract A new method for the calculation of bond orders in alternant hydrocarbons is presented. The method requires a summation over the contributions of various superposition diagrams. Quantitatively, the method is almost as reliable as PPP, and due to its simplicity it can be used for fast and relatively accurate calculation of bond orders. In addition some simple rules are derived, which in many cases can be used to predict the signs of bond orders between nonbonded atoms.
    Type of Medium: Electronic Resource
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  • 7
    Electronic Resource
    Electronic Resource
    Springer
    Theoretical chemistry accounts 76 (1989), S. 331-351 
    ISSN: 1432-2234
    Keywords: Generalized perturbed eigenvalue equation ; Low rank perturbation ; Piecewise local perturbations ; Non-Hermitian matrices
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary The problem of finding eigenvalues and eigenstates of the generalized perturbed eigenvalue equation $$\left( {\mathbb{B} + \mathbb{V}} \right)$$ Ψ = g3(ℂ+ℙ)Ψ is considered. The eigenvalues and the eigenstates of the unperturbed eigenvalue equation $$\mathbb{B}$$ φ = λℂφ are assumed to be known. Matrices $$\mathbb{B},\mathbb{V}$$ , ℂ and ℙ can be arbitrary, except for the requirement that ℂ be nonsingular and that the eigenstates of the unperturbed equation be complete. It is shown that the eigenvalues and the eigenstates of the perturbed equation can be easily obtained if the rank of the generalized perturbation $$\left\{ {\mathbb{V},\mathbb{P}} \right\}$$ , ℙ is small. A special case of low rank perturbations are piecewise local perturbations which are common in physics and chemistry. If the perturbation is piecewise local with fixed localizability, the operation count for the derivation of a single eigenvalue and/or a single eigenstate is $$\mathcal{O}$$ (n). If the perturbation has a fixed rank, the operation count for the derivation of all eigenvalues and/or all eigenstates is $$\mathcal{O}$$ (n 2).
    Type of Medium: Electronic Resource
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  • 8
    ISSN: 1432-2234
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 9
    Electronic Resource
    Electronic Resource
    Springer
    Theoretical chemistry accounts 65 (1984), S. 151-157 
    ISSN: 1432-2234
    Keywords: Bond length alternation ; molecular orbital resonance theory
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract It is shown that in treating bond distortions in the framework of the approach suggested by Nakajima, the contributions of different terms to the total energy are highly sensitive to the choice of parameters and to variations in the functional dependence of the resonance integral as a function of bond length. Hence one can not unambiguously attribute the overall effect to any particular term or terms, and sometimes one has to make a rather careful adjustment in order to avoid qualitatively erroneous results. Though the simple molecular orbital resonance theory (MORT) approach is rather naive, it correctly predicts relative bond lengths in a range of molecules with essentially no parameter adjustment. This approach is hence a rather successful first order approximation to more sophisticated models which progressively incorporate missing contributions. The variation of the resonance integral with bond length and the σ-bond compression energy should be in these more sophisticated models undoubtedly taken into account. However, the contribution of the charge polarisation can not be totally disregarded, especially in the case of conjugated compounds containing small rings.
    Type of Medium: Electronic Resource
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  • 10
    Electronic Resource
    Electronic Resource
    Springer
    Theoretical chemistry accounts 62 (1983), S. 335-350 
    ISSN: 1432-2234
    Keywords: Molecular orbital resonance theory ; Hückel rule ; Charge polarization ; Double bond fixation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract An alternative approach to the treatment of the quantum chemical problems combining both, the MO and VB theory, is proposed. This approach retains the concept of resonance from the VB method, but it treats each particular bond in the MO sense. The method is illustrated with a few examples. Relative stabilities of benzene, pentalene and cyclobutadiene are derived. A Hückel (4m + 2) rule is derived for the annulenes. The charge polarisation in the case of the pentalene molecule is explained. A distortion of the pentalene molecule is considered and it is shown that within this approach the distortion depends on the charge polarisation.
    Type of Medium: Electronic Resource
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