Coupled-cluster theory based upon the fragment molecular-orbital method

Abstract

The fragment molecular-orbital (FMO) method was combined with the single-reference coupled-cluster (CC) theory. The developed method (FMO-CC) was applied at the CCSD and CCSD(T) levels of theory, for the cc-pVnZ family of basis sets (n=D,T,Q) to water clusters and glycine oligomers (up to 32 molecules/residues using as large basis sets as possible for the given system). The two- and three-body FMO-CC results are discussed at length, with emphasis on the basis-set dependence and three-body effects. Two- and three-body approximations based on interfragment distances were developed and the values appropriate for their accurate application carefully determined. The error in recovering the correlation energy was several millihartree for the two-body FMO-CC method and in the submillihartree range for the three-body FMO-CC method. In the largest calculations, we were able to perform the CCSD(T) calculations of (H2O)32 with the cc-pVQZ basis set (3680 basis functions) and (GLY)32 with the cc-VDZ basis set (712 correlated electrons). FMO-CC was parallelized using the upper level of the two-layer parallelization scheme. The computational scaling of the two-body FMO-CC method was demonstrated to be nearly linear. As an example of timings, CCSD(T) calculations of (H2O)32 with cc-pVDZ took 13 min on an eight node 3.2-GHz Pentium4 cluster.