Electronic excitations in the condensed phase play a central role in several fields of modern chemical research, ranging from light-harvesting chromophores in biochemical systems to ultrafast excitations in all facets of time-domain spectroscopy. In each of these areas, the chemical system exhibits a multitude of interactions (both classical and quantum) between different chemical interfaces that give rise to the experimentally-observed spectrum. These many-body interactions are particularly crucial in the liquid phase, as these effects are significantly more complex than in either gas-phase or solid-state systems.<br/><br/>In this talk, a new microscopic picture of solute-solvent electron dynamics and solvatochromic effects is presented, which is uncovered using a new real-time quantum dynamics approach for large solvated systems. In particular, we show that a complex interplay of quantum interactions underlies our observations of solute-solvent effects in a solvated donor-acceptor system. Our ability to probe extremely large systems allows us to highlight the unusual many-body mechanisms that mediate solvatochromic shifts in both nonpolar and polar solvent – without recourse to empirically-derived continuum models. Moreover, our time-domain studies of these solvated systems provide a natural approach to probe in microscopic detail the time-dependent electron dynamics and couplings between the solute and solvent in emergent order.

Electron dynamics of large systems from real-time TDDFTB

251st National Meeting (2016)

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