Ionization potentials and electron affinities from reduced density matrix functional theory

Abstract

In the recent work of S. Sharma \emph{et al.}, (arxiv.org: 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.

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Cited by in corpus (3)

• Local reduced-density-matrix-functional theory: Incorporating static correlation effects in Kohn-Sham equations
• Robust Validation Of Approximate 1-Matrix Functionals With Few-Electron Harmonium Atoms
• Time-dependent renormalized natural orbital theory applied to the two-electron spin-singlet case: ground state, linear response, and autoionization