Solving the Schrödinger equation of molecules by relaxing the antisymmetry rule: Interexchange theory
The Schrödinger equation (SE) and the antisymmetry principle constitute the governing principle of chemistry. A general method of solving the SE was presented before as the free complement (FC) theory, which gave highly accurate solutions for small atoms and molecules. We assume here to use the FC theory starting from the local valence bond wave function. When this theory is applied to larger molecules, antisymmetrizations of electronic wave functions become timeconsuming and therefore, an additional breakthrough is necessary concerning the antisymmetry principle. Usually, in molecular calculations, we first construct the wave function to satisfy the antisymmetry rule, “electronic wave functions must be prescribed to be antisymmetric for all exchanges of electrons, otherwise bosonic interference may disturb the basis of the science.” Starting from determinantal wave functions is typical. Here, we give an antisymmetrization theory, called interexchange (iExg) theory, by dividing molecular antisymmetrizations to those within atoms and between atoms. For the electrons belonging to distant atoms in a molecule, only partial antisymmetrizations or even no antisymmetrizations are necessary, depending on the distance between the atoms. So, the above antisymmetry rule is not necessarily followed strictly to get the results of a desired accuracy. For this and other reasons, the necessarymore »
 Authors:

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 Quantum Chemistry Research Institute, Kyodai Katsura Venture Plaza 107, Goryo Oohara 136, Nishikyoku, Kyoto 6158245 (Japan)
 Publication Date:
 OSTI Identifier:
 22415784
 Resource Type:
 Journal Article
 Resource Relation:
 Journal Name: Journal of Chemical Physics; Journal Volume: 142; Journal Issue: 19; Other Information: (c) 2015 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA)
 Country of Publication:
 United States
 Language:
 English
 Subject:
 37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ACCURACY; ATOMS; BASES; CHEMISTRY; ELECTRONS; INTERFERENCE; MATHEMATICAL SOLUTIONS; MOLECULES; OPERATION; SCHROEDINGER EQUATION; VALENCE; WAVE FUNCTIONS