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Issue 40, 2015
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Time-resolved photoionization spectroscopy of mixed Rydberg-valence states: indole case study

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Abstract

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/πσ* state is revealed. This includes population residing on the excited state surface at large N–H separations for a relatively long period of time (∼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.

Graphical abstract: Time-resolved photoionization spectroscopy of mixed Rydberg-valence states: indole case study

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Article information


Submitted
05 Aug 2015
Accepted
10 Sep 2015
First published
22 Sep 2015

Phys. Chem. Chem. Phys., 2015,17, 26659-26669
Article type
Paper
Author version available

Time-resolved photoionization spectroscopy of mixed Rydberg-valence states: indole case study

M. M. Zawadzki, J. O. F. Thompson, E. A. Burgess, M. J. Paterson and D. Townsend, Phys. Chem. Chem. Phys., 2015, 17, 26659
DOI: 10.1039/C5CP04645A

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