A non-orthogonal Kohn-Sham method using partially fixed molecular orbitals |
| |
Authors: | Kazushi Sorakubo Takeshi Yanai Kenichi Nakayama Muneaki Kamiya Haruyuki Nakano Kimihiko Hirao |
| |
Institution: | (1) Department of Applied Chemistry, School of Engineering, University of Tokyo, Tokyo , 113–8656, Japan |
| |
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. |
| |
Keywords: | Non-orthogonal Kohn-Sham method – Partially fixed molecular orbital (PFMO) – Extreme localized molecular orbital (ELMO) |
本文献已被 SpringerLink 等数据库收录! |
|