Development of a simultaneously frequency- and time-resolved Raman-induced Kerr effect probe.

We detail the development of an optical probe technique based on time-resolved Raman-induced Kerr effect polarization spectroscopy (tr-RIKES). This technique, termed fs/ps RIKES, combines an ultrafast pump pulse with a narrowband probe that directly allows spectral resolution of low-frequency (0-600 cm(-1)) modes typically observable via RIKES. The narrowband probe pulse alleviates the need to scan the time delay between pump and probe pulses to observe molecular coherences, thus making this multiplexed technique a convenient probe for studying low-frequency molecular dynamics. An important distinguishing characteristic of this polarization-sensitive technique arises from the fact that the delay between the impulsive pump pulse and the picosecond-duration probe pulse is optimized to maximize suppression of nonresonant background signal. Model systems, including the rotational spectrum of gas-phase hydrogen and the low-frequency vibrational spectrum of neat bromoform, are used to compare fs/ps RIKES with the conventional time-resolved RIKES technique.