Excited state calculations in solution within the framework of a continuum model of solvation can be performed with two approaches: State-Specific (SS) and Linear-Response (LR). In the former, the solvent polarization depends on the excited state density while, in the latter, it depends on the response of the ground state density to the external field. The SS approach is more physical but more computationally demanding, since only one excited state at a time can be considered. The LR approach, on the other hand, allows to consider multiple states at once and a proper definition of transition properties.  In this contribution, a comparison between the two approaches is carried out by combining the polarizable continuum model of solvation (PCM) and the accurate equation of motion coupled cluster singles and doubles method (EOM-CCSD). Theory and numerical examples are discussed.

Comparison of the linear-response and state-specific approaches for transition energies in solution with the EOM-CCSD-PCM method

246th National Meeting (2013)

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