화학공학소재연구정보센터
Journal of Chemical Physics, Vol.115, No.9, 4212-4222, 2001
Ultrafast dichroism spectroscopy of anthracene in solution. 1. Inertial versus diffusive rotation in benzyl alcohol
Dichroism experiments with 150 fs time resolution on anthracene in benzyl alcohol are presented as a function of viscosity from 14.4 cP (274 K) to 2.7 cP (329 K). These measurements test a qualitative prediction of the viscoelastic picture of liquid dynamics, specifically that earlier "inertial" dynamics have a viscosity independent rate, whereas later "diffusive" dynamics have a rate directly proportional to viscosity. This paper focuses on two components of the dichroism decay that are assigned to rotational motion. A third component is assigned to electronic-state solvation and is analyzed in a companion paper [J. Chem. Phys. 115, 4231 (2001)]. The longest component is due to rotational diffusion and is very well described by a hydrodynamic model with slip boundary conditions. A fast decay component in the subpicosecond region is found and shown to have a viscosity-independent rate. It is assigned to inertial rotation by comparison to the computer simulations of Jas et al. [J. Chem. Phys. 107, 8800 (1997)]. Inertial rotation extends out to at least 1 ps, longer than the range commonly assumed for inertial dynamics. Over much of this range, the inertial rotation is not free-rotor-like, but is strongly modified by interaction with the solvent. The inertial rotation also accounts for the "missing" anisotropy found when the rotational diffusion fits are extrapolated to zero time.