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

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posted on 2023-06-09, 16:20 authored by Adam Baskerville, Andrew W King, Hazel CoxHazel Cox
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.

Funding

Fundamental Studies of Electron Correlation with Applications to DFT; G2355; EPSRC; EP/R011265/1

History

Publication status

  • Published

File Version

  • Published version

Journal

Royal Society Open Science

ISSN

2054-5703

Publisher

The Royal Society

Issue

1

Volume

6

Page range

181357 1-12

Department affiliated with

  • Chemistry Publications

Full text available

  • Yes

Peer reviewed?

  • Yes

Legacy Posted Date

2018-12-21

First Open Access (FOA) Date

2019-01-14

First Compliant Deposit (FCD) Date

2019-01-14

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