Ionization potentials and electron affinities from reduced-density-matrix functional theory

E. N. Zarkadoula*, S. Sharma, J. K. Dewhurst, E. K.U. Gross, N. N. Lathiotakis

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

15 Scopus citations

Abstract

In the recent work of S. Sharma (e-print arXiv:0912.1118), a single-electron spectrum associated with the natural orbitals was defined as the derivative of the total energy with respect to the occupation numbers at half filling for the orbital of interest. This idea reproduces the bands of various periodic systems using the appropriate functional quite accurately. In the present work we apply this approximation to the calculation of the ionization potentials and electron affinities of molecular systems using various functionals within the reduced-density-matrix functional theory. We demonstrate that this approximation is very successful in general and in particular for certain functionals it performs better than the direct determination of the ionization potentials and electron affinities through the calculation of positive and negative ions respectively. The reason for this is identified to be the inaccuracy that arises from different handling of the open- and closed-shell systems.

Original languageAmerican English
Article number032504
JournalPhysical Review A - Atomic, Molecular, and Optical Physics
Volume85
Issue number3
DOIs
StatePublished - 5 Mar 2012
Externally publishedYes

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