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Ultrafast decay of the excited singlet states of thioxanthone by internal conversion and intersystem crossing

Angulo, Gonzalo
Serrano-Andrés, Luis
Rubio-Pons, Oscar
Jacques, Patrice
Published in ChemPhysChem. 2010, vol. 11, no. 2, p. 480-488
Abstract The experimental ultrafast photophysics of thioxanthone in several aprotic organic solvents at room temperature is presented, measured using femtosecond transient absorption together with high-level ab initio CASPT2 calculations of the singlet- and triplet-state manifolds in the gas phase, including computed state minima and conical intersections, transition energies, oscillator strengths, and spin-orbit coupling terms. The initially populated singlet pipi* state is shown to decay through internal conversion and intersystem crossing processes via intermediate npi* singlet and triplet states, respectively. Two easily accessible conical intersections explain the favorable internal conversion rates and low fluorescence quantum yields in nonpolar media. The presence of a singlet-triplet crossing near the singlet pipi* minimum and the large spin-orbit coupling terms also rationalize the high intersystem crossing rates. A phenomenological kinetic scheme is proposed that accounts for the decrease in internal conversion and intersystem crossing (i.e. the very large experimental crescendo of the fluorescence quantum yield) with the increase of solvent polarity.
Keywords Ab initio calculationsConical intersectionsPhotophysicsSolvent effectsTransition states
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Research group Groupe Vauthey
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ANGULO, Gonzalo et al. Ultrafast decay of the excited singlet states of thioxanthone by internal conversion and intersystem crossing. In: ChemPhysChem, 2010, vol. 11, n° 2, p. 480-488. doi: 10.1002/cphc.200900654 https://archive-ouverte.unige.ch/unige:5125

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Deposited on : 2010-02-09

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