Femtosecond Stimulated Raman Scattering Picosecond Molecular Thermometry in Condensed Phases

We demonstrate the capability of femtosecond stimulated Raman scattering (FSRS) data to measure the temperature of condensed matter at the molecular vibrational level. We report the temperature dependence of Raman loss to Raman gain ratios for low frequency modes (< 300 cm(-1)) in a CaCO(3) single crystal from cryogenic to room temperature, which is shown to be in agreement with theoretical predictions. We also report the measurements of nonequilibrium time evolution of mode specific vibrational temperatures in the CaCO(3) single crystal to demonstrate that FSRS can measure temperature on picosecond time scales. Finally, we point out the unique origin of this temperature dependent anti-Stokes to Stokes ratio in stimulated Raman, which is not present in other coherent Raman spectroscopies. These measurements require no material dependent parameters or prior calibration.