Explicitly Correlated Methods within the ccCA Methodology.

Abstract

The prediction of energetic properties within "chemical accuracy" (1 kcal mol(-1) from well-established experiment) can be a major challenge in computational quantum chemistry due to the computational requirements (computer time, memory, and disk space) needed to achieve this level of accuracy. Methodologies such as coupled cluster with single, double, and perturbative triple excitations (CCSD(T)) combined with very large basis sets are often required to reach this level of accuracy. Unfortunately, such calculations quickly become cost prohibitive as system size increases. Our group has developed an ab initio composite method, the correlation consistent Composite Approach (ccCA), which enables such accuracy to be possible, on average, but at reduced computational cost as compared with CCSD(T) in combination with a large basis set. While ccCA has proven quite useful, computational bottlenecks still occur. In this study, the means to reduce the computational cost of ccCA without compromising accuracy by utilizing explicitly correlated methods within ccCA have been considered, and an alternative formulation is described.