Fully optimized implementation of the cluster‐in‐molecule local correlation approach for electron correlation calculations of large systems. Issue 10 (26th October 2018)

• Record Type: Journal Article
• Authors: Ni, Zhigang; Li, Wei; Li, Shuhua
• Other Names: Mo Yirong guestEditor.; Wu Wei guestEditor.; Cao Zexing guestEditor.
• Is Part Of: Journal of computational chemistry. Volume 40:Issue 10(2019)
• Page Start: 1130
• Page End: 1140
• Publication Date: 2018-10-26
• Subjects: local correlation -- cluster‐in‐molecule -- second‐order Møller‐Plesset perturbation theory -- coupled cluster -- large systems; Chemistry -- Data processing -- Periodicals; 542.85
• DOI: 10.1002/jcc.25730
• Languages: English
• ISSNs: 0192-8651

Abstract

Abstract : A fully optimized implementation of the cluster‐in‐molecule (CIM) local correlation method for faster and more accurate electron correlation calculations of large systems is reported. The speedup comes from the new procedure of constructing virtual localized molecular orbitals of clusters. In the new procedure, Boughton–Pulay projection method is employed instead of a much more expensive Boys localization procedure. In addition, basis set superposition error correction for binding energy calculations and parallelized electron correlation calculations of clusters are now implemented. Benchmark calculations and illustrative applications at the Møller–Plesset perturbation theory, coupled cluster singles and doubles (CCSD), and CCSD with perturbative triples correction levels show that this newly optimized CIM approach is a reliable theoretical tool for electron correlation calculations of various large chemical systems. © 2018 Wiley Periodicals, Inc. Abstract : The cluster‐in‐molecule approach is a linear scaling method for electron correlation calculation of large systems. The correlation energy of the whole system is expressed as the contributions from all occupied localized molecular orbitals (LMOs). A fast procedure of constructing virtual LMOs of clusters is proposed. In this procedure, the Boughton–Pulay projection method is employed instead of a much more expensive Boys localization procedure proposed previously.