Distributions of r 1·r 2 and p 1·p 2 in atoms

Joshua W. Hollett; Peter M.W. Gill

doi:10.1021/ct300218c

Distributions of r ₁·r ₂ and p ₁·p ₂ in atoms

Joshua W. Hollett^*, Peter M.W. Gill

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

6 Citations (Scopus)

Abstract

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).

Original language	English
Pages (from-to)	1657-1662
Number of pages	6
Journal	Journal of Chemical Theory and Computation
Volume	8
Issue number	5
DOIs	https://doi.org/10.1021/ct300218c
Publication status	Published - 8 May 2012

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title = "Distributions of r 1·r 2 and p 1·p 2 in atoms",

abstract = "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).",

author = "Hollett, \{Joshua W.\} and Gill, \{Peter M.W.\}",

year = "2012",

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doi = "10.1021/ct300218c",

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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 - https://www.scopus.com/pages/publications/84860751300

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 -

Distributions of r ₁·r ₂ and p ₁·p ₂ in atoms

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