Solvation dynamics: improved reproduction of the time-dependent Stokes shift with polarizable empirical force field chromophore models

Abstract

The inclusion of polarizability slows down the computed solvation dynamics due to interactions of induced dipoles, improving agreement to experiment.

Quantum and semiclassical dynamical studies of nonadiabatic processes in solution: achievements and perspectives

“…In this case this phenomenon occurs because solute/solvent mutual polarization stabilizes Spp* more than Snp*. This finding further highlights the importance of mutual solute/solvent polarization when studying excitedstates properties and dynamics, in line with the indications arising from the analysis of solvent shifts, 216,217 dynamical Stokes shifts, 41 and electronic spectra and dynamics. 136 A similar MQC approach is adopted in ref.…”

“…As a consequence, this can be a critical point also for the methods including explicitly solvent molecules in the dynamics simulation, since they are usually described by empirical FFs. In this respect, the advances in the development and use of polarizable FFs 35,41,223 are surely promising, at least in the case where electrostatic terms are those ruling solute-solvent interactions. However, as mentioned above, to be applied to nonadiabatic dynamics, they require a SS description.…”

“…It is clear that many dynamical spectral parameters, e.g. time-resolved dynamic Stokes shift, are ruled by solvation dynamics, and their analysis, by using either continuum 37,38 or explicit solvation models, [39][40][41] can give crucial insights on the interplay between ultrafast electronic relaxation of solute and solvent molecules. Nonetheless, due to their large number, we shall not discuss the studies aimed essentially to include solvent effects in the calculations of the PES or the related spectral parameters (for example, the vertical absorption or emission energies 42 ), as well as excited-state dynamical studies that do not explicitly address nonadiabatic processes, but focus on solvent relaxation (e.g.…”

White light employing luminescent engineered large (mega) Stokes shift molecules: a review

“…There are other factors that could affect the Stokes shi value and emission shiing of compounds, including solvation dynamic, 54,154 pH effect, 155 temperature, 156,157 polymer dispersion, 158 and others. Therefore, the incorporation of different components of Stokes shi entails a joint venture of consideration between the molecular conformation and its nanoenvironments.…”

Enantiomerization of Axially Chiral Biphenyls: Polarizable MD Simulations in Water and Butylmethylether

“…Lennard-Jones parameters were not optimized, but taken from the CHARMM Drude force field. Atomic polarizabilities and charges in gas phase were computed according to protocols described in detail in references [ 63 , 64 , 65 ] using geometries optimized at the RI-MP2/6-31+G(d) level of theory: Atomic polarizabilities were obtained on the RI-MP2/Sadlej-TZ level of theory using the methodology described in references [ 63 , 64 , 65 ]. According to suggestions in reference [ 42 ], polarizabilities were subsequently scaled by empirical factors, 0.85 for the cation, 0.724 for anion 1 and 0.6 for anion 2 .…”