The ultrafast dynamics of liquid CBrCl3studied with optical Kerr effect and Raman scattering

The ultrafast inter- and intramolecular dynamics of liquid CBrCl3 are studied with a femtosecond laser in a pump/probe optical Kerr experiment. The prompt part of the observed Kerr signal is found to comprise not just electronic response but also coherent coupling. As reported in the literature, the weak and delayed part of the signal is attributed to three kinds of intermolecular dynamics: diffusive reorientation, polarizability distortion, and molecular libration with decay times, respectively, of 2 ps, 500 fs, and 190 fs. Included in the delayed Kerr signal are long lasting oscillations which are ascribed to quantum interference involving four normal vibrations of the molecule. By a careful fitting of both the time domain (Kerr) and frequency domain (Raman) data with existing theories the four vibrations are identified as ν2 = 422 cm−1, ν3 = 246 cm−1, ν5 = 295 cm−1, and ν6 = 191 cm−1, with dephasing times, 1.1 ps, 1.7 ps, 1 ps, and 1 ps, respectively.