THE DYNAMICS OF SUCCINONITRILE IN THE PLASTIC PHASE BY SUBPICOSECOND TIME-RESOLVED OPTICAL KERR EFFECT

The relaxation kinetics of succinonitrile in the plastic crystalline phase has been investigated between 250 and 320 K by transient optical Kerr effect with femtosecond pulses. Three different noninstantaneous contributions to the signal time profile have been identified. The fastest one is a subpicosecond decay, attributed to the relaxation of the damped librational and torsional vibrations of the molecules. The intermediate decay time, ranging from 4 ps at 323 K to 30 ps at 250 K, is interpreted as due to rotations of the trans molecules about the shortest inertia axis which bring the molecule from one cube diagonal to another. The slowest decay time ranges from 28 ps at 323 K to 190 ps at 250 K and agrees very well with previous measurements with different experimental techniques. This decay is interpreted as due mostly to rotational motions of the gauche molecules jumping from one equilibrium position to another in the unit cell. The activation energy for the two processes is 3.7 and 4.3 kcal/mol, respectively, for the intermediate and slow kinetics.