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Incomplete basis set problem. IV. Perturbative corrections to pair energies
Author(s) -
McDowell Keith
Publication year - 1980
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.560170505
Subject(s) - hamiltonian (control theory) , basis set , basis (linear algebra) , perturbation (astronomy) , ground state , perturbation theory (quantum mechanics) , physics , complement (music) , statistical physics , quantum mechanics , mathematics , molecule , chemistry , geometry , mathematical optimization , biochemistry , complementation , gene , phenotype
A partitioning of the molecular Hamiltonian into the occupied and virtual orbital spaces and their orthogonal complement is introduced and used to develop a perturbation expansion of the exact ground‐state energy relative to the Hartree–Fock energy computed using an incomplete basis set. The leading perturbation corrections to pair energies due to using the incomplete basis set are considered in detail. Summations of certain classes of pair contributions are discussed and a resummed correction is obtained.