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Simultaneous determination of nuclear and electronic wave functions without Born–Oppenheimer approximation: Ab initio NO+MO/HF theory
Author(s) -
Nakai Hiromi
Publication year - 2001
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.1106
Subject(s) - wave function , born–oppenheimer approximation , ab initio , chemistry , quantum , function (biology) , quantum mechanics , physics , atomic physics , molecule , evolutionary biology , biology
We develop a simultaneous determination method of nuclear and electronic wave functions without the Born–Oppenheimer approximation. We examine two expanding methods, namely, molecular orbital (MO)‐type and valence bond (VB)‐type expansions for a nuclear orbital, which is a one‐particle wave function of a nucleus. The VB‐type expansion is shown to be more accurate than the MO‐type one because of the local nature of the nuclei. We also investigate the basis function expansion of the nuclear orbital and propose a scheme to determine the orbital exponent for the nuclear basis function. Numerical calculations confirm the accuracy and feasibility of the present method. © 2001 John Wiley & Sons, Inc. Int J Quantum Chem, 2001