1997
DOI: 10.1002/bbpc.19971010304
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State‐resolved intramolecular dynamics in highly excited HOCl

Abstract: The features and mechanisms of intramolecular energy redistribution (IVR) and state mixing of HOCl at chemically significant energies have been investigated using intra-cavity laser absorption spectroscopy (ICLAS). These studies revealed that for the observed vibrational states up to about 75% of the dissociation energy E, both strong and weak interactions (Fermi-type, Coriolis) exist but producing only localized perturbations in the spectra. The 5 v, band, however, at about 85% of the dissociation threshold E… Show more

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Cited by 29 publications
(22 citation statements)
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“…Furthermore, the inter-and intramolecular potentials are simply not known well enough and introduce significant uncertainty and ambiguity. These limitations and the present experimental results, which suggest that mechanisms of IVR in isolated molecules [113] may to some extent survive in solution, encouraged us to propose a model, originally developed for the gas phase. This model can be used to explain and partly predict IVR in weakly interacting solvents.…”
Section: Theoretical Approaches To Ivr and Vet In Solutionmentioning
confidence: 89%
“…Furthermore, the inter-and intramolecular potentials are simply not known well enough and introduce significant uncertainty and ambiguity. These limitations and the present experimental results, which suggest that mechanisms of IVR in isolated molecules [113] may to some extent survive in solution, encouraged us to propose a model, originally developed for the gas phase. This model can be used to explain and partly predict IVR in weakly interacting solvents.…”
Section: Theoretical Approaches To Ivr and Vet In Solutionmentioning
confidence: 89%
“…Using a simplified two-state interaction model, Abel and co-workers 5,11,13 have assigned a number of ''dark'' states based on the effect they cause on the spectra of nearby ''bright'' states. In particular, they suggested that the 213 state is a perturber of the ''bright'' 300 state.…”
Section: Dipole Moments and Ir Transition Intensitiesmentioning
confidence: 99%
“…From these experiments the dissociation energy and band origins for the 6 1 and 7 1 overtones have been accurately determined. A number of ''dark'' states have also been assigned by Abel and co-workers 5,11,13 based on the effect of these states on the nearby ''bright'' states.…”
Section: Introductionmentioning
confidence: 99%
“…1,2 In these experiments, the rotationally state-selected J and K states of 6 OH are prepared by a double-resonance technique, and a high resolution absorption spectrum determined. The analysis of these and other spectra 3 indicates that Coriolis coupling is very small for the observed states, and further that the HOCl is a near prolate symmetric top, and thus J and K are good quantum numbers. These rotationally excited states are metastable, and their very long lifetimes ͑ca.…”
Section: Introductionmentioning
confidence: 73%