Abstract
The frequency-resolved, molecular-beam spectrum of the O–H stretch of ethanol near 3678 cm−1 has been measured at 10 MHz resolution using an electric-resonance optothermal spectrometer (EROS). A portion of the R branch of the predominantly a-type O–H stretch for the more stable trans conformer has been rotationally assigned using a high-sensitivity infrared-microwave double-resonance technique. The spectrum shows extensive near-resonant perturbations that characterize the intramolecular vibrational energy redistribution (IVR) process. Single rovibrational transitions of the O–H stretch normal mode are found to be fractionated into more than 60 transitions due to the coupling of the O–H stretch to the background of nearby vibrational states. The overall width of the collection of molecular eigenstates coming from a single zeroth-order rovibrational state in the vibrationally excited state gives a 25 ps lifetime for energy redistribution from the O–H stretch in trans-ethanol. This lifetime is in reasonable agreement with previous time-resolved measurements of the O–H stretch lifetime of 70 ps for ethanol in CCl4. Comparison of the two measurement techniques is discussed.
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