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 have extended to molecules a density functional previously parametrized for atomic computations. The Coulomb-hole-Hartree-Fock functional, introduced by Clementi in 1963, estimates the dynamical correlation energy by the computations of a Hartree-Fock-type single-determinant wave function, where the Hartree-Fock potential was augmented with an effective potential term, related to a hard Coulomb hole enclosing each electron. The method was later revisited by S. Chakravorty and E. Clementi [Phys. Rev. A 39, 2290 (1989)], where a Yukawa-type soft Coulomb hole replaced the previous hard hole; atomic correlation energies, computed for atoms with Z = 2 to Z = 54 as well as for a number of excited states, validated the method. In this article, we parametrized a function, which controls the width of the soft Coulomb hole, by fitting the first and second atomic ionization potentials of the atoms with 1 ≤ Z ≤ 18. The parametrization has been preliminarily validated by computing the dissociation energy for a number of molecules. A few-determinant version of the Coulomb-hole-Hartree-Fock method, necessary to account for the nondynamic correlation corrections, is briefly discussed. © 1994 John Wiley & Sons, Inc.
Zusätzliches Material:
4 Ill.
Materialart:
Digitale Medien
URL:
http://dx.doi.org/10.1002/qua.560520413
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