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On assessing functional errors in density functional theory using atomisation energies and electric field gradients

Lookup NU author(s): Josh Littlefair, Dr Daniel ColeORCiD, Professor Thomas Penfold


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Despite the exact form of Exc being unknown, remarkably simple approximations can provide unrivaled accuracy to cost ratio. Both physically and empirically motivated approaches for developing Exc are used, but nearly all focus upon improving calculated energies. Herein we simultaneously study energy and density errors associated with a range of density functionals for CuCl and four related complexes. Atomisation energies are compared with high-level coupled cluster, CCSD(T), while computed electric field gradients are compared with those obtained from microwave spectroscopy and CCSD(T). We show that simple metrics are able to reveal the relative contributions of the energetic errors associated with the use of an approximate density and an approximate exchange and correlation functional. The methods adopted provide a potentially useful approach for assessing and developing new balanced functionals that are able to provide simultaneous improvement in both energetics and properties associated with the electron density.

Publication metadata

Author(s): Littlefair J, Cole DJ, Penfold TJ

Publication type: Article

Publication status: Published

Journal: International Journal of Quantum Chemistry

Year: 2021

Volume: 121

Issue: 23

Print publication date: 05/12/2021

Online publication date: 16/08/2021

Acceptance date: 30/07/2021

ISSN (print): 0020-7608

ISSN (electronic): 1097-461X

Publisher: Wiley


DOI: 10.1002/qua.26799


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