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Reduced hamiltonian orbitals. I. a new approach to the many‐electron problem
Author(s) -
Absar Ilyas,
Coleman A. J.
Publication year - 2009
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.560100836
Subject(s) - atomic orbital , hamiltonian (control theory) , electron , physics , quantum mechanics , mathematics , mathematical optimization
The partitioning of energy into 0‐energy, 1‐energy, and 2‐energy is developed. A new definition of correlation energy as the 2‐energy is proposed. The natural orbitals of the 1‐energy operator are discussed. These reduced Hamiltonian orbitals are uniquely determined by a one‐step diagonalization procedure and correspond to an independent‐particle model suitable simultaneously for ground as well as excited states. Minimum basis set calculations are presented for LiH and H 2 O and compared with similar SCF and basis orbital studies.