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Structure of the triplet excited state of bromanil from time-resolved resonance Raman spectra and simulation

Puranik, Mrinalini and Umapathy, Siva and Snijders, Jaap G and Chandrasekhar, Jayaraman (2001) Structure of the triplet excited state of bromanil from time-resolved resonance Raman spectra and simulation. In: Journal of Chemical Physics, 115 (13). pp. 6106-6114.

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Abstract

Time-resolved resonance Raman (TR3) spectroscopy has been used to study the structure of the triplet excited state of bromanil. These experimental results were then simulated using parameters from density functional theoretical (DFT) calculations and wave packet dynamics, in order to understand the structure and mode-specific displacements of the resonant excited state. The transition dipole moments and the energy separation of the T1 and Tn states were obtained from time-dependent DFT calculations. We have demonstrated application of the technique to tetrabromo-p-benzoquinone. From our calculations, the observed T1 \rightarrow Tn absorption spectrum has been assigned to the 3Bg \rightarrow 3Bu transition. The geometry has been optimized for the resonant higher triplet state, Tn, and is found to be in good agreement with the predictions of the wave packet dynamical simulations. Mode-specific displacements of the triplet state geometry have been obtained from simulations and these have been rationalized with respect to the molecular orbital involved. Thus, we have demonstrated that from the simulations of the experimental TR3 spectral data, valuable additional information can be derived on the structure of the transient states that may then be used for elucidation of structure-reactivity correlation in the future.

Item Type: Journal Article
Additional Information: Copyright for this article belongs to American Institute of Physics (AIP).
Department/Centre: Division of Chemical Sciences > Organic Chemistry
Division of Chemical Sciences > Inorganic & Physical Chemistry
Date Deposited: 16 Dec 2004
Last Modified: 19 Sep 2010 04:17
URI: http://eprints.iisc.ernet.in/id/eprint/2463

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