Ab initio correlated valence shell effective Hamiltonian method for atomic and molecular systems

Journal Article · Mon Jul 01 04:00:00 EDT 1991 · Journal of Chemical Physics; (USA)

DOI:https://doi.org/10.1063/1.461441· OSTI ID:5467708

Banerjee, A ^[1]

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1. Theoretical Chemistry Project, Idaho National Engineering Laboratory, EG G Idaho, Inc., P. O. Box 1625, Idaho Falls, Idaho 83415-2208 (USA)

A new method for correlated electronic structure calculations that makes explicit reference to {ital valence} electrons only is presented for atomic and molecular processes in which the core electrons remain inert. The method is based on constructing a valence Hamiltonian that includes a one-electron effective potential for the core--valence interactions. It {ital exactly} reproduces {ital all} properties (wave functions, energies, etc.) of an all electron calculation with frozen core wave functions with same bases. It has no adjustable parameters, and no restrictions on the choice of basis sets. It yields considerable savings of computer time and space over the corresponding all electron calculations. Self-consistent field (SCF) and complete active space multiconfiguration self-consistent field (CAS-MCSCF) test calculations on ground states of {ital F}, {ital F}{sup {minus}}, and {ital S} are presented.

• DOE Contract Number: AC07-76ID01570
• OSTI ID: 5467708
• Journal Information: Journal of Chemical Physics; (USA), Journal Name: Journal of Chemical Physics; (USA) Vol. 95:1; ISSN JCPSA; ISSN 0021-9606
• Country of Publication: United States
• Language: English

Related Subjects

640302* -- Atomic
Molecular & Chemical Physics-- Atomic & Molecular Properties & Theory
74 ATOMIC AND MOLECULAR PHYSICS
ATOMS
CONFIGURATION INTERACTION
ELECTRONIC STRUCTURE
FUNCTIONS
HAMILTONIAN FUNCTION
MOLECULES
SELF-CONSISTENT FIELD
VALENCE