화학공학소재연구정보센터
Journal of Chemical Physics, Vol.114, No.23, 10252-10264, 2001
Introduction of n-electron valence states for multireference perturbation theory
The present work presents three second-order perturbative developments from a complete active space (CAS) zero-order wave function, which are strictly additive with respect to molecular dissociation and intruder state free. They differ by the degree of contraction of the outer-space perturbers. Two types of zero-order Hamiltonians are proposed, both are bielectronic, incorporating the interactions between electrons in the active orbitals, therefore introducing a rational balance between the zero-order wave function and the outer-space. The use of Dyall's Hamiltonian, which puts the active electrons in a fixed core field, and of a partially contracted formalism seems a promising compromise. The formalism is generalizable to multireference spaces which are parts of a GAS. A few test applications of the simplest variant developed in this paper illustrate its potentialities.