Second-Order Perturbation Theory with Fractional Charges and Fractional Spins.

Published

Journal Article

In this work the behavior of MP2 for fractional occupations is investigated. The consideration of fractional charge behavior gives a simple derivation of an expression for the chemical potential (or the derivative of energy with respect to the number of electrons) of MP2. A generalized optimized effective potential formalism (OEP) has been developed in which the OEP is a nonlocal potential, which can be applied to explicit functionals of the orbitals and eigenvalues and also facilitates the evaluation of the chemical potential. The MP2 derivative improves upon the corresponding Koopmans' theorem in Hartree-Fock theory for the ionization energy and also gives a good estimate of the electron affinity. In strongly correlated systems with degeneracies and fractional spins, MP2 diverges, and another corrected second-order perturbative method ameliorates this failure for the energy but still does not recapture the correct behavior for the energy derivatives that yield the gap. Overall we present a view of wave function based methods and their behavior for fractional charges and spins that offers insight into the application of these methods to challenging chemical problems.

Full Text

Duke Authors

Cited Authors

  • Cohen, AJ; Mori-Sánchez, P; Yang, W

Published Date

  • April 2009

Published In

Volume / Issue

  • 5 / 4

Start / End Page

  • 786 - 792

PubMed ID

  • 26609584

Pubmed Central ID

  • 26609584

Electronic International Standard Serial Number (EISSN)

  • 1549-9626

International Standard Serial Number (ISSN)

  • 1549-9618

Digital Object Identifier (DOI)

  • 10.1021/ct8005419

Language

  • eng