How polarizabilities and C-6 coefficients actually vary with atomic volume

作者：Gould Tim^*

来源：Journal of Chemical Physics, 2016, 145(8): 084308.

DOI：10.1063/1.4961643

In this work, we investigate how atomic C-6 coefficients and static dipole polarizabilities alpha scale with effective volume. We show, using confined atoms covering rows 1-5 of the periodic table, that C-6/C-6(R) approximate to (V/V-R)(pZ) and alpha/alpha(R) approximate to (V/V-R)(p)'(Z) (for volume V = integral dr4 pi/3 r(3)n(r)), where C-6(R), alpha(R), and V-R are the reference values and effective volume of the free atom. The scaling exponents p(Z) and p'(Z) vary substantially as a function of element number Z = N, in contrast to the standard "rule of thumb" that p(Z) = 2 and p'(Z) = 1. Remarkably, we find that the polarizability and C6 exponents p' and p are related by p' approximate to p - 0.615 rather than the expected p' approximate to p/2. Results are largely independent of the form of the confining potential (harmonic, cubic, and quartic potentials are considered) and kernel approximation, justifying this analysis. Published by AIP Publishing.

• 出版日期2016-8-28