Journal of Physical Chemistry, Vol.98, No.1, 313-320, 1994
Effects of Local Liquid Structure on Orientational Relaxation - 2-Ethylnaphthalene, Neat and in Solution
The rotational dynamics of 2-ethylnaphthalene have been studied using subpicosecond transient grating optical Kerr effect techniques. Botb the neat liquid and a series of dilutions in carbon tetrachloride were examined. The neat liquid was studied over a temperature range of 2-100-degrees-C, and the 1 M solution was studied from -30 to +25-degrees-C. After ultrafast librational dynamics have decayed, there remains (>2 ps) in the neat liquid a triple-exponential decay of the orientational anisotropy. The slower two decays exhibit hydrodynamic temperature dependences, corresponding to rotational diffusion. The fastest decay is not hydrodynamic, being temperature independent from 2 to 40-degrees-C. This decay is attributed to the relaxation dynamics of local structures in the liquid and is not present in all but the highest concentration (5 M) solution.
Keywords:IMPULSIVE STIMULATED SCATTERING;ROTATIONAL FRICTION COEFFICIENTS;DEPOLARIZED RAYLEIGH-SCATTERING;OPTICAL KERR DYNAMICS;MOLECULAR-DYNAMICS;LIGHT-SCATTERING;BOUNDARY-CONDITION;LIBRATIONAL MODEL;CS2 LIQUID;REORIENTATION