TY - JOUR
T1 - Distributions of r 1·r 2 and p 1·p 2 in atoms
AU - Hollett, Joshua W.
AU - Gill, Peter M.W.
PY - 2012/5/8
Y1 - 2012/5/8
N2 - We consider the two-electron position and momentum dot products, α = r 1·r 2 and β = p 1·p 2, and present a method for extracting their distributions, A(α) and B(β), from molecular wave functions built on Gaussian basis functions. The characteristics of the Hartree-Fock A HF(α) and B HF(β) 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, δA(α) ≡ A(α) - A HF(α) and δB(β) ≡ B(β) - B HF(β), 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(α), A HF(α), B(β), and B HF(β).
AB - We consider the two-electron position and momentum dot products, α = r 1·r 2 and β = p 1·p 2, and present a method for extracting their distributions, A(α) and B(β), from molecular wave functions built on Gaussian basis functions. The characteristics of the Hartree-Fock A HF(α) and B HF(β) 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, δA(α) ≡ A(α) - A HF(α) and δB(β) ≡ B(β) - B HF(β), 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(α), A HF(α), B(β), and B HF(β).
UR - http://www.scopus.com/inward/record.url?scp=84860751300&partnerID=8YFLogxK
U2 - 10.1021/ct300218c
DO - 10.1021/ct300218c
M3 - Article
SN - 1549-9618
VL - 8
SP - 1657
EP - 1662
JO - Journal of Chemical Theory and Computation
JF - Journal of Chemical Theory and Computation
IS - 5
ER -