Real-Time Quantum Dynamics Reveals Complex, Many-Body Interactions in Solvated Nanodroplets

MARÍA BELÉN OVIEDO; BRYAN M. WONG

JOURNAL OF CHEMICAL THEORY AND COMPUTATION

AMER CHEMICAL SOC

Lugar: Washington; Año: 2016

1549-9618

lectronic excitations in the liquid phase are surprisingly rich and considerably more complex than either gas-phase or solid-state systems. While the majority of physical and biological processes take place in solvent, our understanding of nonequilibrium excited-state processes in these condensed phase environments remains far from complete. A central and long-standing issue in these solvated environments is the assessment of many-body interactions, particularly when the entire system is out of equilibrium and many quantum states participate in the overall process. Here we present a microscopic picture of solute?solvent electron dynamics and solvatochromic effects, which we uncover using a new real-time quantum dynamics approach for extremely large solvated nanodroplets. In particular, we find that a complex interplay of quantum interactions underlies our observations of solute?solvent effects, and simple macroscopic solvatochromic shifts can even be qualitatively different at the mic