Abstract
The polarization dependence of vibrational coupling signals seen in femtosecond stimulated Raman spectroscopy (FSRS) is investigated. Changing the polarization of a pulse used to impulsively excite coherent low frequency chlorine bending motion in CD Cl3 has a dramatic effect on the line shape of vibrational sidebands which arise from the anharmonic coupling of the pumped modes at 262 and 365 cm-1 with the higher frequency symmetric stretching mode at 652 cm-1. The asymmetric bend sideband (652+262 cm-1) changes sign and magnitude as the impulsive pulse polarization is rotated relative to the Raman pulses, while the symmetric bend sideband (652+365 cm-1) is relatively polarization independent. These experiments demonstrate the ability of FSRS to obtain time-resolved information on not only the vibrational coupling strength but also the symmetry of anharmonically coupled modes.
Original language | English (US) |
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Article number | 124501 |
Journal | Journal of Chemical Physics |
Volume | 127 |
Issue number | 12 |
DOIs | |
State | Published - 2007 |