An approximate diatomics in molecules formulation of generalized valence bond theory.
The slow computational speed of the generalized valence bond perfect pairing method (GVB-PP) has been an impediment to its routine use. We have addressed this problem by employing a diatomics in molecules Hamiltonian derived from a second quantization perturbation approach. This results in all three- and four-centered two-electron integrals being dropped from the traditional GVB-PP calculation. For moderate sized molecules, as for example C20 computed with a double zeta + polarization basis, there is on average a fifty-fold decrease in computational times. In this article, we present the theory behind our approach and analyze the accuracy and speed of this approximate GVB-PP method for several cases where density functional methods have produced ambivalent results.
Department of Chemistry, University of Manitoba, Winnipeg, Manitoba, Canada R3T 2N2. cullen@cc.umanitoba.ca
John
J
Cullen
D003201:Computers; D005029:Ethylenediamines / Q000737:chemistry; D007536:Isomerism; D008345:Manganese / Q000737:chemistry; D008956:Models, Chemical; D013997:Time Factors
D005029:Ethylenediamines; D008345:Manganese; C011452:disalicylaldehyde ethylenediamine