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Vibrational coherence refers to a collective coherence among an ensemble of molecules and is a consequence of optical excitation on a time scale faster than the motion of interest. A short optical pulse also excites a manifold of quantized vibrational levels in a single molecule. These vibrational levels are coherent because they have specific phase and amplitude relations and therefore constitute a nonstationary vibrational state or wave packet that describes the nuclear motion. The vibrational coherence resulting from impulsive excitation reflects the nonstationary wave packet dynamics of individual molecules. Under continuous-wave excitation, vibrational coherence is not initiated in the ensemble. Nevertheless, the nonstationary wave packet dynamics of individual rhodopsin molecules are identical to that indicated by the femtosecond experiments.
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We thank Continuum Corporation for loaning us the MACH 500 YAG laser used for some of this work and S. J. Rosenthal for helpful discussions. This research was supported by Department of Energy contract DE-AC03-76SF00098 (C.V.S.), National Institutes of Health grant EY-02051 (R.A.M.), and National Science Foundation grant CHE 91-20254 (R.A.M.).
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