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 direct method to optimize parameters in nonorthogonal basis orbitals is discussed. The partial derivatives of the energy of the state of interest, not necessarily the ground state, with respect to the orbital parameters are calculated analytically. The required cofactors up to third order of the overlap matrices over spin-space orbitals in pairs of Slater determinants are calculated by biorthogonalization. All parameters are varied simultaneiously in the direction of the negative gradient (steepest descent). A search logic with dynamically adjusted step-size is shown, in the example of the minimum basis Ne ground state, to find the energy minimum in an efficient manner.
Additional Material:
3 Tab.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/qua.560100114
