Intraatomic correlation correction in the FORS model

Journal Article · Thu May 23 04:00:00 UTC 1985 · J. Phys. Chem.; (United States)

DOI:https://doi.org/10.1021/j100257a017· OSTI ID:5133773

Lam, B; Schmidt, M W; Ruedenberg, K

Wave functions in the full optimized reaction space (FORS) can be expressed in terms of localized configuration-generating MO's which have essentially atomic character. It is therefore possible to construct from them deformed atomic configuration state functions and from these, in turn, antisymmetrized products of deformed atomic state functions. These composite functions (CF's) form an alternate basis for the full reaction space, and they can be considered as the optimal intrinsic basis for implementation of the deformed-atoms-in-molecules approach of Moffitt, Hurley, and Arai. The FORS composite functions have the further advantage of forming an orthonormal set, a circumstance which simplifies introduction of the intraatomic correlation corrections conceptually as well as operationally, since there is no need for additional assumptions to compensate for the nonorthogonality of the composite functions. The mathematical formalism for a general application of this method and, in particular, the operational specifics of the transformation from molecular antisymmetrized orbital products to composite functions of atomic states are explicitly developed. Tables facilitating this transformation are given for all atomic valence states arising from the configuration s/sup n/p/sup m/. An application to the ground-state of NH is presented. 47 references, 1 figure, 7 tables.

• Research Organization: Ames Lab., IA
• OSTI ID: 5133773
• Journal Information: J. Phys. Chem.; (United States), Journal Name: J. Phys. Chem.; (United States) Vol. 89:11; ISSN JPCHA
• Country of Publication: United States
• Language: English

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74 ATOMIC AND MOLECULAR PHYSICS
ALKALI METAL COMPOUNDS
ALKALINE EARTH METAL COMPOUNDS
ATOMIC MODELS
BERYLLIUM COMPOUNDS
BORON COMPOUNDS
CARBON COMPOUNDS
CORRELATION FUNCTIONS
DATA
FIELD THEORIES
FLUORINE COMPOUNDS
FUNCTIONS
GENERAL RELATIVITY THEORY
HALOGEN COMPOUNDS
HELIUM COMPOUNDS
HYDROGEN COMPOUNDS
INFORMATION
LITHIUM COMPOUNDS
MATHEMATICAL MODELS
MECHANICS
MOLECULAR MODELS
MOLECULAR ORBITAL METHOD
NEON COMPOUNDS
NITROGEN COMPOUNDS
NUMERICAL DATA
ORTHOGONAL TRANSFORMATIONS
OXYGEN COMPOUNDS
QUANTUM MECHANICS
RARE GAS COMPOUNDS
RELATIVITY THEORY
THEORETICAL DATA
TRANSFORMATIONS
WAVE FUNCTIONS