A non-orthogonal Kohn-Sham method using partially fixed molecular orbitals

Kazushi Sorakubo, Takeshi Yanai, Kenichi Nakayama, Muneaki Kamiya, Haruyuki Nakano, Kimihiko Hirao

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Abstract

A density functional theory method using partially fixed molecular orbitals (PFMOs) is presented. The PFMOs, which have some fixed molecular orbital coefficients and are non-orthogonal, are a generalization of the extreme localized orbitals (ELMOs) of Couty, Bayse, and Hall (1997) Theor Chem Acc 97:96. A non-orthogonal Kohn-Sham method with these PFMOs is derived, and is applied to molecular calculations on the ionization potential of pyridine, the energy difference between cis- and trans-butadiene, the reaction barrier height of the cyclobutene-cis-butadiene interconversion, and the potential energy curve of the hydrogen shift reaction of hydroxycarbene to formaldehyde. The PFMO Kohn-Sham method reproduces well the results of the full Kohn-Sham method without having a restriction on the molecular orbital coefficients. The difference is less than 0.1 eV in the ionization potential and about 0.1 kcal/mol in the barrier height and in the potential energy calculations.

Original languageEnglish
Pages (from-to)328-337
Number of pages10
JournalTheoretical Chemistry Accounts
Volume110
Issue number5
DOIs
Publication statusPublished - Dec 1 2003
Externally publishedYes

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All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry

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