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 R12 basis set incompleteness correction. Four test cases are examined to measure the performance of the LMRCI+R12 (without and with the Davidson + Q correction for size-extensivity) and LMRACPF+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+R12/LMRCI+Q+R12/LMRACPF+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+R12/LMRCI+Q+R12/LMRACPF+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).
All Science Journal Classification (ASJC) codes
- Computer Science Applications
- Physical and Theoretical Chemistry