Excited electronic states of fenchone, thiofenchone, and selenofenchone are characterized and assigned with different gas-phase spectroscopic methods and \textit{ab initio} quantum chemical calculations. With an increasing atomic number of the chalcogen, we observe increasing bathochromic (red) shifts, which vary in strength for Rydberg states, valence-excited states, and ionization energies. The spectroscopic insight is used to state-resolve the contributions in multi-photon photoelectron circular dichroism with femtosecond laser pulses. This is shown to be a sensitive observable of molecular chirality in all studied chalcogenofenchones. Our work contributes new spectroscopic information, particularly on thiofenchone and selenofenchone. It may open a perspective for future coherent control experiments exploiting resonances in the visible and or near-ultraviolet spectral regions.
@article{arxiv.2503.14261,
title = {Excited state assignment and state-resolved photoelectron circular dichroism in chalcogen-substituted fenchones},
author = {Sudheendran Vasudevan and Steffen M. Giesen and Simon T. Ranecky and Lutz Marder and Igor Vidanović and Manjinder Kour and Catmarna Küstner-Wetekam and Nicolas Ladda and Sagnik Das and Tonio Rosen and Vidana Popkova and Hangyeol Lee and Denis Kargin and Tim Schäfer and Andreas Hans and Thomas Baumert and Robert Berger and Hendrike Braun and Arno Ehresmann and Guido W. Fuchs and Thomas F. Giesen and Jochen Mikosch and Rudolf Pietschnig and Arne Senftleben},
journal= {arXiv preprint arXiv:2503.14261},
year = {2025}
}