Development of coherent Raman measurements of temperature in condensed phases

We report theoretical considerations and preliminary data on various forms of coherent Raman spectroscopy that have been considered as candidates for measurement of temperature in condensed phase experiments with picosecond time resolution. Due to the inherent broadness and congestion of vibrational features in condensed phase solids, particularly at high temperatures and pressures, only approaches that rely on the ratio of anti-Stokes to Stokes spectral features are considered. Methods that rely on resolution of vibrational progressions, calibration of frequency shifts with temperature and pressure in reference experiments, or detailed comparison to calculation are inappropriate or impossible for our applications. In particular, we consider femtosecond stimulated Raman spectroscopy (FSRS), femtosecond/picosecond hybrid coherent Raman spectroscopy (multiplex CARS), and optical heterodyne detected femtosecond Raman induced Kerr Effect spectroscopy (OHD-FRIKES). We show that only FSRS has the ability to measure temperature via an anti-Stokes to Stokes ratio of peaks.