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.
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Acknowledgments.
This research was supported in part by a Grant-in-Aid for Specially Promoted Research, “Simulations and Dynamics of Real Molecular Systems,” from the Ministry of Education, Culture, Sports, Science and Technology of Japan, and a Grant-in-Aid for Scientific Research (C) to HN and a Research Fellowship for Young Scientists to TY, which were both from the Japan Society for the Promotion of Science.
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Sorakubo, K., Yanai, T., Nakayama, K. et al. A non-orthogonal Kohn-Sham method using partially fixed molecular orbitals. Theor Chem Acc 110, 328–337 (2003). https://doi.org/10.1007/s00214-003-0477-8
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DOI: https://doi.org/10.1007/s00214-003-0477-8