Journal
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
Volume 17, Issue 40, Pages 26659-26669Publisher
ROYAL SOC CHEMISTRY
DOI: 10.1039/c5cp04645a
Keywords
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Funding
- European Research Council under the European Union [258990]
- Heriot-Watt University
- EPSRC [EP/G041717/1, EP/K021052/1] Funding Source: UKRI
- Engineering and Physical Sciences Research Council [EP/G041717/1, EP/K021052/1, 1155678] Funding Source: researchfish
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Time-resolved photoelectron imaging was used to study non-adiabatic relaxation dynamics in gas-phase indole following photo-excitation at 267 nm and 258 nm. Our data analysis was supported by various ab initio calculations using both coupled cluster and density functional methods. The highly differential energy-and angle-resolved information provided by our experimental approach provides extremely subtle details of the complex interactions occurring between several low-lying electronically excited states. In particular, new insight into the role and fate of the mixed Rydberg-valence 3s/pi sigma* state is revealed. This includes population residing on the excited state surface at large N-H separations for a relatively long period of time (similar to 1 ps) prior to dissociation and/or internal conversion. Our findings may, in part, be rationalized by considering the rapid evolution of this state's electronic character as the N-H stretching coordinate is extended - as extensively demonstrated in the supporting theory. Overall, our findings highlight a number of important general caveats regarding the nature of mixed Rydberg-valence excited states, their spectral signatures and detection sensitivity in photoionization measurements, and the evaluation of their overall importance in mediating electronic relaxation in a wide range of small model-chromophore systems providing bio-molecular analogues - a topic of considerable interest within the chemical dynamics community over the last decade.
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