ISSN:
0020-7608
Schlagwort(e):
Computational Chemistry and Molecular Modeling
;
Atomic, Molecular and Optical Physics
Quelle:
Wiley InterScience Backfile Collection 1832-2000
Thema:
Chemie und Pharmazie
Notizen:
We examine various perturbation-variational approximations for molecular electronic energy when the fifth-order perturbational energies are available. Such theories require very little additional computation once the sequence of perturbation energies are known yet supply a bound even when the peturbation sequence is poorly convergent. We choose for computational examples results obtained very rapidly from a zeroth order wave function consisting of doubly occupied localized bonds and examine polarization within these bonds, delocalization, and bond breaking. In general, we find that the fifth-order energy itself, and especially the [2, 1] Padé approximant on this sequence, are especially accurate in estimating the total energy and more accurate than any variational scheme when the zeroth order localized wave function is a good description of the electronic structure. The variational results, however, are nearly as accurate, and a [1, 0] Padé on the sequence of variational results is remarkably robust, even in those cases where the perturbation sequence is poorly defined.We also examine several scaling techniques, or partitionings of the Hamiltonian. Although these scaling techniques do accelerate convergence of the perturbation sequence, none that we examine give better results, than the [2, 1] padé, which is independent of any scaling.
Zusätzliches Material:
2 Ill.
Materialart:
Digitale Medien
URL:
http://dx.doi.org/10.1002/qua.560330502
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