Coupled cluster (CC) theory provides one of the most reliable quantum chemistry methods to evaluate the electronic structure and response properties of molecules. Nevertheless, accurate calculations on isolated systems are not enough for realistic simulations of their properties in solution.  In fact, the solvent influences the solute geometry, electronic structure, and response to external fields.<br/>We have developed the theory and the computer code for the combination of the CC with single and double excitations (CCSD) method, and polarizable solvation models. Our methods are applicable to both ground and excited state problems, including the analytic evaluation of energy gradients for geometry optimization and linear response tensors. The approximation to the complete theory that we have devised allow for CCSD calculations in solution at a cost that is comparable to that of gas phase CC theory, thus making this level of theory affordable for applications in the condensed phase where most chemistry occurs.<br/>We have extended our methods to combine CCSD with both implicit and explicit polarizable solvation models simultaneously. This allows the molecular treatment of the first few explicit solvation shells while bulk solvation is handled with a continuum model. Thus, we can account for direct solute-solvent interactions (e.g., hydrogen bonds) while limiting the number of solvent configurations necessary for statistical averaging.<br/>We have computed ground state minimum geometries and solvation free energies, although most of out work has focused on excited state properties. Indeed, we have computed both absorption and emission spectra of solvated systems, and we reproduced experimental relative solvent shifts. We have also studied frequency dependent properties like polarizabilities and specific rotation. For the latter, for instance, we have shown that solvent effects can account for the correct sign of the specific rotation while the same CCSD calculation in the gas phase failed.<br/>

Robust and efficient coupled cluster-polarizable solvation methods for electronic molecular properties in the condensed phase

249th National Meeting (2015)

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