Electron correlation in Li+, He, H− and the critical nuclear charge system ZC: energies, densities and Coulomb holes

Baskerville, Adam L, King, Andrew W and Cox, Hazel (2019) Electron correlation in Li+, He, H− and the critical nuclear charge system ZC: energies, densities and Coulomb holes. Royal Society Open Science, 6 (1). 181357 1-12. ISSN 2054-5703

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Abstract

This paper presents high accuracy correlation energies, intracule densities and Coulomb hole(s) for the lithium cation, helium, hydride ion and the system with the critical nuclear charge, Z_C, for binding two electrons. The fully-correlated (FC) wavefunction and the Hartree-Fock (HF) wavefunction are both determined using a Laguerre-based wavefunction. It is found that for the lithium cation and the helium atom a secondary Coulomb hole is present, in agreement with a previous literature finding, confirming a counter-intuitive conclusion that electron correlation can act to bring distant electrons closer together. However, no evidence for a tertiary Coulomb hole is found. For the hydride anion and the system just prior to electron detachment only a single Coulomb hole is present and electron correlation decreases the probability of finding the electrons closer together at all radial distances. The emergence of a secondary Coulomb hole is investigated and found to occur between Z =1.15 and 1.20.
The FC and HF energies and intracule densities (in atomic units) used to calculate the correlation energy and Coulomb hole respectively, are accurate to at least the nano-scale for helium and the cation and at least the micro-scale for the anions.

Item Type: Article
Keywords: Electron correlation, Coulomb hole, Intracules, Critical Nuclear Charge
Schools and Departments: School of Life Sciences > Chemistry
Related URLs:
Depositing User: Hazel Cox
Date Deposited: 21 Dec 2018 12:37
Last Modified: 01 Jul 2019 20:00
URI: http://sro.sussex.ac.uk/id/eprint/80942

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Project NameSussex Project NumberFunderFunder Ref
Fundamental Studies of Electron Correlation with Applications to DFTG2355EPSRCEP/R011265/1