ChemInform Abstract: VIBRATIONAL AND ROTATIONAL SPECTROSCOPY OF THE FIRST ELECTRONICALLY ALLOWED TRANSITION OF α‐DICARBONYLS

Gurnick, M.; Chaiken, J.; Benson, Thomas; McDonald, James H.

doi:10.1002/chin.198118049

Cited by 1 publication

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“…Good candidates for observing isc effects are the -dicarbonyls, whose spectra range from the small molecule limit to the intermediate limit. 26 The spectra and selective excitation dynamics of these molecules have been studied extensively,26,27 and it is known that states of the lowest excited singlet manifold are coupled to a sparse set of triplet states so that isc does not occur irreversibly in (isolated) molecules such as glyoxal and methylglyoxal. McDonald et al 26 have observed quantum beats on the microsecond time scale in the fluorescence spectra which, together with the closely spaced resonances in the excitation spectra, suggest that laser intensity effects may be observable.…”

Section: Discussionmentioning

confidence: 99%

Laser intensity induced nonradiative processes in molecules

Needham¹,

Rhodes²

1981

J. Phys. Chem.

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The effects of the coupling strength (i.e., the Rabí frequency) of a coherent radiation mode interacting with a multilevel molecule are considered. A doorway-state basis is used in which the radiative doorway state, carrying all of the radiative interaction strength from the ground (initial) state, is coupled by intramolecular (nonradiative) interaction to other excited states. The resulting coupling scheme involves an effective Hamiltonian formulation in an extended rotating basis. Quantitative results from the theory are obtained by computer simulation. It is shown how variation of the laser coupling strength can modify the dynamics of nonradiative transitions, thereby producing (1) decoupling of radiationless decay, (2) enhancement of radiationless decay, (3) selectivity of photophysical and photochemical processes, or (4) laser-induced isolation of states, depending on the conditions of the system. The case of two states coupled through a common manifold of states and the conditions for biexponential decay are also considered.

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Section: Discussionmentioning

confidence: 99%