Asymptotic Exchange Energy of Heteronuclear Dimers

• Published in: The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Vol. 115; no. 25; pp. 7346 - 7351
• Main Authors: Yiu, C. L, Tang, K. T, Greenwood, W. G
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 30.06.2011
• ISSN: 1089-5639; 1520-5215
• DOI: 10.1021/jp2010925

A simple expression for the asymptotic exchange energy of heteronuclear dimers is derived from the surface integral method. A five-dimensional hypersurface, consisting of all spherical surfaces centered at the nucleus of the atom with higher ionization energy, more appropriate for the case where the two atoms have different ionization energies, is used in the surface integral. All integrals are carried out analytically. Compared with the exchange energy of Smirnov and Chibisov, which is also obtained from the surface integral method with a hypersurface consisting of all infinite planes perpendicular to the internuclear axis, the present result is much simpler. The exchange energies of alkali hydrides are computed as an illustration. It is shown that the present method and the method of Smirnov and Chibisov are complementary to each other.