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Electron correlation in Li+, He, H- and the critical nuclear charge system ZC: energies, densities and Coulomb holes
journal contribution
posted on 2023-06-09, 16:20 authored by Adam Baskerville, Andrew W King, Hazel CoxHazel CoxThis 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 ScienceISSN
2054-5703Publisher
The Royal SocietyExternal DOI
Issue
1Volume
6Page range
181357 1-12Department affiliated with
- Chemistry Publications
Full text available
- Yes
Peer reviewed?
- Yes
Legacy Posted Date
2018-12-21First Open Access (FOA) Date
2019-01-14First Compliant Deposit (FCD) Date
2019-01-14Usage metrics
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