Distributions of r(1).r(2) and p(1).p(2) in Atoms

作者：Hollet Joshua W^*; Gill Peter M W

来源：Journal of Chemical Theory and Computation, 2012, 8(5): 1657-1662.

DOI：10.1021/ct300218c

We consider the two-electron position and momentum dot products, alpha = r(1).r(2) and beta = p(1).p(2), and present a method for extracting their distributions, A(alpha) and B(beta), from molecular wave functions built on Gaussian basis functions. The characteristics of the Hartree-Fock A(HF)(alpha) and B-HF(beta) for He and the first-row atoms are investigated, with particular attention to the effects of Pauli exchange. The effects of electron correlation are studied via the holes, Delta A(alpha) equivalent to A(alpha) - A(HF)(alpha) and Delta B(beta) equivalent to B(beta) - B-HF(beta), and the hole structures are rationalized in terms of radial and angular correlation effects. Correlation effects are also examined through an analysis of the first moments of A(alpha), A(HF)(alpha), B(beta), and B-HF(beta).

• 出版日期2012-5