ISSN:
0020-7608
Keywords:
Computational Chemistry and Molecular Modeling
;
Atomic, Molecular and Optical Physics
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
The evaluation of interatomic interactions at large separations (R) typically involves neglecting electron exchange, treating the Coulomb interaction between atoms as a perturbation, neglecting third- and higher-order energy contributions, and approximating the Coulomb interaction by a short expansion in spherical harmonics and, usually, powers of R-1. This last approximation, using an approximate perturbing Hamiltonian to evaluate a second-order perturbed energy, is examined here; error bounds and a simple correction are introduced. Three illustrative applications to the H—H+ interaction are given: the error incurred by truncating the spherical-harmonic expansion is bounded, the R-1 expansion is corrected for the overlap of the “atomic” charge distributions, and the R-1 expansion is analyzed to see why it works as well as it does.
Additional Material:
3 Tab.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/qua.560100305
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