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 general method is presented to find in a least-squares sense a set of orthogonal eigenfunctions and their eigenvalues from local energy and numerical integration methods or by any other dissymmetric approach to solve the eigenvalue problem of a Hermitian operator. By this method a generalization of the minimum variance method to more than one eigenfunction is obtained, which is a variant of Scott's method. Also a new method is derived - called the minimum-overlap method - that is a least-squares numerical version of the standard Rayleigh-Ritz method. Test calculations on the atoms Be and Tm and the molecules H2 and CO have been performed with both numerical Hartree-Fock and Hartree-Fock-Slater methods. The least-squares solutions are an improvement over other methods in the case of accurate basis sets. Numerical Hartree-Fock calculations of moderate accuracy are found to be considerably faster than the analytic method.
Additional Material:
6 Tab.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/qua.560280410
