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Coupled‐cluster theory for the polarizable continuum model. III. A response theory for molecules in solution
Author(s) -
Cammi R.
Publication year - 2012
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.23271
Subject(s) - coupled cluster , polarizable continuum model , solvation , excited state , excitation , polarizability , non equilibrium thermodynamics , linear response theory , density functional theory , chemistry , quadratic equation , molecule , physics , statistical physics , quantum mechanics , computational chemistry , mathematics , condensed matter physics , geometry
A coupled‐cluster (CC) response functions theory for molecular solutes described with the framework of the polarizable continuum model (PCM) is presented. The theory is an extension to the dynamical molecular properties of the PCM‐CC analytic derivatives recently proposed for the calculation of static molecular properties (Cammi, Jr Chem Phys 2009, 131, 164104). The theory is presented for linear and quadratic response functions, and the operative expressions of these response functions can accurately account for the nonequilibrium solvation effects. The excitation energies and transition moments of the solvated chromophores have been determined from the linear response functions. Accurate expressions for gradients of excitation energies for the evaluation of the excited state properties have been also discussed. © 2012 Wiley Periodicals, Inc. Int J Quantum Chem, 2012