An implicit solvent model is applied to the calculation of chiroptical properties at the coupled cluster level for molecules particularly sensitive to the solvent environment. The solvation model used here is based on a smooth definition of the dielectric function, constructed directly from the solute quantum mechanical electronic density. Solute-solvent interactions are captured by solving the nonhomogenous Poisson equation on a real-space grid and incorporated into the molecular Hamiltonian self-consistently for subsequent coupled cluster calculations. Linear response and equation-of-motion approaches are utilized to compute specific rotation values and electronic circular dichroism (ECD) spectra in a variety of solvents at the coupled-cluster singles and doubles (CCSD) level for a series of molecules exhibiting large solvation effects, including methyloxirane, norbornenone, and dimethylallene. To address the inherent shortcomings of a continuum solvation model, the effects of short-range hydrogen bonding interactions are investigated with the inclusion of explicit solvent molecules in conjunction with the implicit model.

Modeling solvent effects on chiroptical response properties with coupled cluster theory and implicit solvation

255th National Meeting (2018)

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