PNOndash;CI (pair natural orbital configuration interaction) and CEPAndash;PNO (coupled electron pair approximation with pair natural orbitals) calculations of molecular systems. I. Outline of the method for closedhyphen;shell states

摘要

The methods of configuration interaction with double substitutions to pair natural orbitals (PNOminus;CI) and of the coupled electron pair approximation (CEPA) proposed by W. Meyer are improved by combination with a new scheme of the calculation of the pair natural orbitals (PNO) and an efficient iterative scheme for the diagonalization of the CI matrix. The relevant matrix elements for the closed shell case are tabulated, the quantities that are pertinent for an analysis of the correlation energy are defined, and the organization of the computer programs is described.