A generalized Heitler--London theory of the chemical bond in H sup + sub 2
- Max-Planck-Institut fuer Stroemungsforschung, Bunsenstrasse 10, D-3400 Goettingen (Germany)
The perturbation theory for the total energies of the 1{ital s}{sigma}{sub {ital g}} and 2{ital p}{sigma}{sub {ital u}} states of H{sup +}{sub 2} is reformulated in a manner which avoids problems resulting from symmetrization. First a new set of localized wave functions are defined and calculated from polarization perturbation theory. After symmetrization of these wave functions, a generalized Heitler--London energy, which can be expanded to all orders, is obtained. In second order the result agrees with the Murrell--Shaw Musher--Amos expression. An expansion of the expectation value of the energy is also carried out and provides similar results. Many symmetry-adapted perturbation results are obtained simply and directly from the present localized wave-function approach. The present theory suggests a novel interpretation of the terms contributing to the total potential energy and helps to rearrange them to give improved results.
- OSTI ID:
- 5289349
- Journal Information:
- Journal of Chemical Physics; (United States), Vol. 95:8; ISSN 0021-9606
- Country of Publication:
- United States
- Language:
- English
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