Acceleration of self‐consistent field convergence in ab initio molecular dynamics simulation with multiconfigurational wave function |
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| Authors: | Masaki Okoshi Hiromi Nakai |
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| Affiliation: | 1. Department of Chemistry and Biochemistry, School of Advanced Science and Engineering, Waseda University, Tokyo, Japan;2. Research Institute for Science and Engineering, Waseda University, Tokyo, Japan;3. CREST, Japan Science and Technology Agency, Saitama, Japan;4. ESICB, Kyoto University, Kyotodaigaku‐Katsura, Kyoto, Japan |
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| Abstract: | The Lagrange interpolation of molecular orbital (LIMO) method, which reduces the number of self‐consistent field iterations in ab initio molecular dynamics simulations with the Hartree–Fock method and the Kohn–Sham density functional theories, is extended to the theory of multiconfigurational wave functions. We examine two types of treatments for the active orbitals that are partially occupied. The first treatment, as denoted by LIMO(C), is a simple application of the conventional LIMO method to the union of the inactive core and the active orbitals. The second, as denoted by LIMO(S), separately treats the inactive core and the active orbitals. Numerical tests to compare the two treatments clarify that LIMO(S) is superior to LIMO(C). Further applications of LIMO(S) to various systems demonstrate its effectiveness and robustness. © 2014 Wiley Periodicals, Inc. |
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| Keywords: | ab initio molecular dynamics simulation acceleration technique self‐consistent field convergence multiconfigurational wave function theory Lagrange interpolation technique |
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