Coupled cluster theory with the polarizable continuum model of solvation. Issue 1 (29th August 2018)

• Record Type: Journal Article
• Authors: Caricato, Marco
• Other Names: Andreussi Oliviero guestEditor.; Frediani Luca guestEditor.; Kulik Heather J. guestEditor.
• Is Part Of: International journal of quantum chemistry. Volume 119:Issue 1(2019)
• Page Start: n/a
• Page End: n/a
• Publication Date: 2018-08-29
• Subjects: coupled cluster -- PCM -- excited states -- linear response -- state specific; Quantum chemistry -- Periodicals; 541.28
• DOI: 10.1002/qua.25710
• Languages: English
• ISSNs: 0020-7608

Abstract

Abstract: The environment may significantly affect molecular properties. Thus, it is desirable to account explicitly for these effects on the wave function and its derivatives, especially when the latter are evaluated with accurate methods, such as those belonging to coupled cluster (CC) theory. In this tutorial review, we discuss how to combine CC methods with the polarizable continuum model of solvation (PCM). We describe useful approximations that include the solvent response to the correlation and excited state equations while maintaining the computational cost comparable to in vacuo calculations. Although applied to PCM, the theoretical framework presented in this review is general and can be used with any polarizable embedding model. Representative applications of the CC‐PCM method to ground and excited state properties of solvated molecules are presented, and comparisons with experiment, and between the full and approximate schemes are discussed. Abstract : In this tutorial review, the theory, implementation, and representative applications for combining coupled cluster theory with the polarizable model of solvation are presented. The equations for the ground state free energy, for excitations within the state specific and linear response formalisms, and for the evaluation of ground state linear response properties are discussed. The focus is on accurate approximations that maintain the cost of the calculation virtually identical to the corresponding one in vacuo.