Journal or Book Title
Journal of Chemical Physics
The effect of replacing the standard single-determinant reference wave functions in variants of G2 and G3 theory by multireference (MR) wave functions based on a full-valence complete active space has been investigated. Twelve methods of this type have been introduced and comparisons, based on a slightly reduced G2-1 test set, are made both internally and with the equivalent single-reference methods. We use CASPT2 as the standard MR-MP2 method and MRCl+Q as the higher correlation procedure in these calculations. We find that MR-G2(MP2,SVP), MR-G2(MP2), and MR-G3(MP2) perform comparably with their single-reference analogs, G2(MP2,SVP), G2(MP2), and G3(MP2), with mean absolute deviations (MADs) from the experimental data of 1.41, 1.54, and 1.23 kcal mol−1, compared with 1.60, 1.59, and 1.19 kcal mol−1, respectively. The additivity assumptions in the MR-Gn methods have been tested by carrying out MR-G2/MRCI+Q and MR-G3/MRCI+Q calculations, which correspond to large-basis-set MRCI+Q+ZPVE+HLC calculations. These give MADs of 1.84 and 1.58 kcal mol−1, respectively, i.e., the agreement with experiment is somewhat worse than that obtained with the MR-G2(MP2) and MR-G3(MP2) methods. In a third series of calculations, we have examined pure MP2 and MR-MP2 analogs of the G2 and G3 procedures by carrying out large-basis-set MP2 and CASPT2(+ZPVE+HLC) calculations. The resultant methods, which we denote G2/MP2, G3/MP2, MR-G2/MP2, and MR-G3/MP2, give MADs of 4.19, 3.36, 2.01, and 1.66 kcal mol−1, respectively. Finally, we have examined the effect of using MCQDPT2 in place of CASPT2 in five of our MR-Gn procedures, and find that there is a small but consistent deterioration in performance. Our calculations suggest that the MR-G3(MP2) and MR-G3/MP2 procedures may be useful in situations where a multireference approach is desirable.
Copyright 2001 American Institute of Physics. This article may be downloaded for personal use only. Any other use requires prior permission of the author and the American Institute of Physics.
American Institute of Physics
Sølling, Theis I.; Smith, David M.; Radom, Leo; Freitag, Mark Alan; and Gordon, Mark S., "Towards Multireference Equivalents of the G2 and G3 Methods" (2001). Chemistry Publications. 393.