Range-separation parameter in tuned exchange–correlation functionals: Successive ionizations and the Fukui function

Gledhill, Jonathan D.; De Proft, Frank; Tozer, David J.

doi:10.1021/acs.jctc.6b00709

Range-separation parameter in tuned exchange–correlation functionals: Successive ionizations and the Fukui function Thumbnail

Authors

Jonathan D. Gledhill

Frank De Proft

Professor David Tozer d.j.tozer@durham.ac.uk
Professor

Abstract

The range-separation parameter in tuned, range-separated exchange–correlation functionals is investigated in two contexts. First, the system dependence of the parameter is investigated for a series of systems obtained by successively ionizing a single species, paying particular attention to the degree of linearity in the energy versus electron number curve. The parameter exhibits significant system dependence and, therefore, achieving near-linearity in one segment of the curve leads to strong nonlinearity in other segments. This provides a challenging test case for the development of new functionals designed to overcome the known problems of this class of functional. Next, the study considers whether a range-separation parameter tuned to a Koopmans energy condition is also applicable for the analogous density condition. This is tested by comparing two formulations of the Fukui function of conceptual density functional theory, for three representative systems. Both formulations yield the same general features and are not highly sensitive to the range-separation parameter. However, the agreement between the two is near-optimal when the energy-tuned parameter is used, indicating that this parameter is applicable for the analogous density condition.

Citation

Gledhill, J. D., De Proft, F., & Tozer, D. J. (2016). Range-separation parameter in tuned exchange–correlation functionals: Successive ionizations and the Fukui function. Journal of Chemical Theory and Computation, 12(10), 4879-4884. https://doi.org/10.1021/acs.jctc.6b00709

Journal Article Type	Article
Acceptance Date	Sep 13, 2016
Online Publication Date	Sep 13, 2016
Publication Date	Oct 11, 2016
Deposit Date	Nov 3, 2016
Publicly Available Date	Sep 13, 2017
Journal	Journal of Chemical Theory and Computation
Print ISSN	1549-9618
Electronic ISSN	1549-9626
Publisher	American Chemical Society
Peer Reviewed	Peer Reviewed
Volume	12
Issue	10
Pages	4879-4884
DOI	https://doi.org/10.1021/acs.jctc.6b00709

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Copyright Statement
This document is the Accepted Manuscript version of a Published Work that appeared in final form in Journal of Chemical Theory and Computation, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://doi.org/10.1021/acs.jctc.6b00709.