The calculation of exchange forces: General results and specific models
Abstract
In order to clarify questions about the calculation of the exchange energy of a homonuclear molecular ion, an analysis is carried out of a model problem consisting of the one-dimensional limit of H2+. It is demonstrated that the use of the infinite polarization expansion for the localized wave function in the Holstein-Herring formula yields an approximate exchange energy which at large internuclear distances R has the correct leading behavior to O(e-R) and is close to but not equal to the exact exchange energy. The extension to the n-dimensional double-well problem is presented.
- Publication:
-
Journal of Chemical Physics
- Pub Date:
- August 1993
- DOI:
- 10.1063/1.465193
- Bibcode:
- 1993JChPh..99.2841S