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

Magdalena M. Zawadzki, James O. F. Thompson, Emma A. Burgess, Martin J. Paterson, David Townsend

Research output: Contribution to journalArticlepeer-review

16 Citations (Scopus)
45 Downloads (Pure)


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.
Original languageEnglish
Pages (from-to)26659-26669
Number of pages11
JournalPhysical Chemistry Chemical Physics
Issue number40
Early online date22 Sept 2015
Publication statusPublished - 2015

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Physics and Astronomy(all)


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