Improved Cluster-in-Molecule Local Correlation Approach for Electron Correlation Calculation of Large Systems

An improved cluster-in-molecule (CIM) local correlation approach is developed to allow electron correlation calculations of large systems more accurate and faster. We have proposed a refined strategy of constructing virtual LMOs of various clusters, which is suitable for basis sets of various types. To recover medium-range electron correlation, which is important for quantitative descriptions of large systems, we find that a larger distance threshold (ξ) is necessary for highly accurate results. Our illustrative calculations show that the present CIM-MP2 (second-order Møller-Plesser perturbation theory, MP2) or CIM-CCSD (coupled cluster singles and doubles, CCSD) scheme with a suitable ξ value is capable of recovering more than 99.8% correlation energies for a wide range of systems at different basis sets. Furthermore, the present CIM-MP2 scheme can provide reliable relative energy differences as the conventional MP2 method for secondary structures of polypeptides