The WKB method for the quantum mechanical two-Coulomb-center problem
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Using a modified perturbation theory, we obtain asymptotic expressions for the two-center quasiradial and quasiangular wave functions for large internuclear distances R. We show that in each order of 1/R, corrections to the wave functions are expressed in terms of a finite number of Coulomb functions with a modified charge. We derive simple analytic expressions for the first, second, and third corrections. We develop a consistent scheme for obtaining WKB expansions for solutions of the quasiangular equation in the quantum mechanical two-Coulomb-center problem. In the framework of this scheme, we construct semiclassical two-center wave functions for large distances between fixed positively charged particles (nuclei) for the entire space of motion of a negatively charged particle (electron). The method ensures simple uniform estimates for eigenfunctions at arbitrary large internuclear distances R, including R ≥ 1. In contrast to perturbation theory, the semiclassical approximation is not related to the smallness of the interaction and hence has a wider applicability domain, which permits investigating qualitative laws for the behavior and properties of quantum mechanical systems.
Keywordssemiclassical approximation WKB method two Coulomb centers asymptotic solution
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