Affordable Access

Publisher Website

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

Authors
Type
Published Article
Journal
ChemPhysChem
1439-7641
Publisher
Wiley Blackwell (John Wiley & Sons)
Publication Date
Volume
11
Issue
2
Pages
480–488
Identifiers
DOI: 10.1002/cphc.200900654
PMID: 20069622
Source
Medline

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 pi pi* state is shown to decay through internal conversion and intersystem crossing processes via intermediate n pi* 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 pi pi* 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.

There are no comments yet on this publication. Be the first to share your thoughts.

Statistics

Seen <100 times
0 Comments