Spin-Free [2]R12 Basis Set Incompleteness Correction to the Local Multireference Configuration Interaction and the Local Multireference Average Coupled Pair Functional Methods

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• 作者：Luke B. Roskop ; Edward F. Valeev ; Emily A. Carter ; Mark S. Gordon ; Theresa L. Windus
• 刊名：Journal of Chemical Theory and Computation
• 出版年：2016
• 出版时间：July 12, 2016
• 年：2016
• 卷：12
• 期：7
• 页码：3176-3184
• 全文大小：481K
• 年卷期：0
• ISSN：1549-9626

文摘

The local multireference configuration interaction (LMRCI) and local multireference averaged coupled pair functional (LMRACPF) methods are extended to include explicit correlation via the universal spin-free [2]_R12 basis set incompleteness correction. Four test cases are examined to measure the performance of the LMRCI+[2]_R12 (without and with the Davidson + Q correction for size-extensivity) and LMRACPF+[2]_R12 methods. These tests examine bond dissociation energies (BDEs) for ethene, perfluoroethene, propene, and 2-butene. As has been demonstrated for other methods, the LMRCI+[2]_R12/LMRCI+Q+[2]_R12/LMRACPF+[2]_R12 BDEs are as accurate as the conventional LMRCI/LMRACPF BDEs that are computed with the basis set one cardinal number higher. It is shown that LMRCI+[2]_R12/LMRCI+Q+[2]_R12/LMRACPF+[2]_R12 BDEs computed with the June calendar basis sets preserve the accuracy of the corresponding BDEs computed with the conventional aug-cc-pVXZ basis sets (where X = D, T, Q).