State-to-state studies of intramolecular dynamics and unimolecular reactions

Double-resonance vibrational overtone excitation spectra of small molecules, in combination with laser-induced fluorescence product detection, provide information on both their energetics and intramolecular energy redistribution dynamics. Application of this approach to measure OH stretch overtone spectra of HOOH and NH2OH near their dissociation threshold provides estimates of the O-O and N-O bond energies of 17051.8 +/- 4 cm(-1) and 21 620 +/- 20 cm(-1) respectively. In symmetrical molecules, such as HOOH, the double-resonance excitation technique allows us to prepare molecules in either pure OH stretch overtone levels or combination levels in which the excitation energy is divided between two identical OH stretch oscillators. Comparison of the resulting vibrational overtone linewidths indicates no clear difference between the pure OH stretch and the local-local combination levels. However, comparison of the energy transfer rates from pure OH stretch vibrations and those in which one quantum of energy is put in a low frequency mode reveals faster rates from the latter. This observation clearly indicates that coupling strengths depend markedly on the vibrational character of the coupling partner and not simply on the total energy. Comparison of the OH stretch overtone spectra of the structurally similar molecules HOOH, NH2OH, and CH3OH reveal similar rates of vibrational energy redistribution, despite the difference in the density of states in these molecules. This observation reinforces the notion that energy flow between the OH stretch and dark background states is not statistical but rather is controlled by coupling to a small subset of background states.

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 Record created 2005-12-15, last modified 2018-03-17

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