The accurate theoretical description of condensed-phase spectroscopy is complicated by both electronic interactions and vibrational interactions.  In this talk, I will describe parallel efforts to treat these two effects with a longer-term goal of their ultimate combination.  Regarding electronic interactions, I will describe the recent development and application of equation-of-motion coupled-cluster theory to linear spectroscopies of condensed-phase systems, such as the paradigmatic uniform electron gas and atomistic semiconductors like diamond and silicon.  These ideas will be generalized to the calculation of higher-order spectroscopies, such as pump-probe and four-wave mixing.  I will finally describe our recent work on the accurate calculation of linear and nonlinear spectroscopies for electronic systems coupled to vibrational degrees of freedom.  The presented approach is based on the careful combination of perturbative master equations and ensemble sampling, which combine to give a potentially first-principles methodology that is in no way restricted to any functional form of the electronic-vibrational interaction.

Towards accurate first-principles spectroscopy in condensed phases

254th National Meeting (2017)

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