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Spin‐component‐scaled electron correlation methods
Author(s) -
Grimme Stefan,
Goerigk Lars,
Fink Reinhold F.
Publication year - 2012
Publication title -
wiley interdisciplinary reviews: computational molecular science
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.126
H-Index - 81
eISSN - 1759-0884
pISSN - 1759-0876
DOI - 10.1002/wcms.1110
Subject(s) - electronic correlation , electronic structure , coupled cluster , perturbation theory (quantum mechanics) , wave function , ab initio , electron , excited state , spin (aerodynamics) , physics , excitation , statistical physics , density functional theory , atomic physics , quantum mechanics , molecule , thermodynamics
Spin‐component‐scaled (SCS) electron correlation methods for electronic structure theory are reviewed. The methods can be derived theoretically by applying special conditions to the underlying wave functions in perturbation theory. They are based on the insight that low‐order wave function expansions treat the correlation effects of electron pairs with opposite spin (OS) and same spin (SS) differently because of their different treatment at the underlying Hartree–Fock level. Physically, this is related to the different average inter‐electronic distances in the SS and OS electron pairs. The overview starts with the original SCS‐MP2 method and discusses its strengths and weaknesses and various ways to parameterize the scaling factors. Extensions to coupled‐cluster and excited state methods as well the connection to virtual‐orbital dependent density functional approaches are highlighted. The performance of various SCS methods in large thermochemical benchmarks and for excitation energies is discussed in comparison with other common electronic structure methods. This article is categorized under: Electronic Structure Theory > Ab Initio Electronic Structure Methods