Solvent response and dielectric relaxation in supercooled butyronitrile.
We have measured the dynamics of solvation of a triplet state probe, quinoxaline, in the glass-forming dipolar liquid butyronitrile near its glass transition temperature T(g)=95 K. The Stokes shift correlation function displays a relaxation time dispersion of considerable magnitude and the optical linewidth changes along the solvation coordinate in a nonmonotonic fashion. These features are characteristic of solvation in viscous solvents and clearly indicate heterogeneous dynamics, i.e., spatially distinct solvent response times. Using the dielectric relaxation data of viscous butyronitrile as input, a microscopic model of dipolar solvation captures the relaxation time, the relaxation dispersion, and the amplitude of the dynamical Stokes shift remarkably well.
Ito
Naoki
N
Department of Chemistry and Biochemistry, Arizona State University, Tempe, AZ 85287-1604, USA.
Duvvuri
Kalyan
K
Matyushov
Dmitry V
DV
Richert
Ranko
R