Excited state assignment and state-resolved photoelectron circular dichroism in chalcogen-substituted fenchones

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Main Authors:	Vasudevan, Sudheendran, Giesen, Steffen M., Ranecky, Simon T., Marder, Lutz, Vidanović, Igor, Kour, Manjinder, Küstner-Wetekam, Catmarna, Ladda, Nicolas, Das, Sagnik, Rosen, Tonio, Popkova, Vidana, Lee, Hangyeol, Kargin, Denis, Schäfer, Tim, Hans, Andreas, Baumert, Thomas, Berger, Robert, Braun, Hendrike, Ehresmann, Arno, Fuchs, Guido W., Giesen, Thomas F., Mikosch, Jochen, Pietschnig, Rudolf, Senftleben, Arne
Format:	Preprint
Published:	2025
Subjects:	Chemical Physics
Online Access:	Acceder al recurso
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author	Vasudevan, Sudheendran Giesen, Steffen M. Ranecky, Simon T. Marder, Lutz Vidanović, Igor Kour, Manjinder Küstner-Wetekam, Catmarna Ladda, Nicolas Das, Sagnik Rosen, Tonio Popkova, Vidana Lee, Hangyeol Kargin, Denis Schäfer, Tim Hans, Andreas Baumert, Thomas Berger, Robert Braun, Hendrike Ehresmann, Arno Fuchs, Guido W. Giesen, Thomas F. Mikosch, Jochen Pietschnig, Rudolf Senftleben, Arne
author_facet	Vasudevan, Sudheendran Giesen, Steffen M. Ranecky, Simon T. Marder, Lutz Vidanović, Igor Kour, Manjinder Küstner-Wetekam, Catmarna Ladda, Nicolas Das, Sagnik Rosen, Tonio Popkova, Vidana Lee, Hangyeol Kargin, Denis Schäfer, Tim Hans, Andreas Baumert, Thomas Berger, Robert Braun, Hendrike Ehresmann, Arno Fuchs, Guido W. Giesen, Thomas F. Mikosch, Jochen Pietschnig, Rudolf Senftleben, Arne
contents	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.
format	Preprint
id	arxiv_https___arxiv_org_abs_2503_14261
institution	arXiv
publishDate	2025
record_format	arxiv
spellingShingle	Excited state assignment and state-resolved photoelectron circular dichroism in chalcogen-substituted fenchones Vasudevan, Sudheendran Giesen, Steffen M. Ranecky, Simon T. Marder, Lutz Vidanović, Igor Kour, Manjinder Küstner-Wetekam, Catmarna Ladda, Nicolas Das, Sagnik Rosen, Tonio Popkova, Vidana Lee, Hangyeol Kargin, Denis Schäfer, Tim Hans, Andreas Baumert, Thomas Berger, Robert Braun, Hendrike Ehresmann, Arno Fuchs, Guido W. Giesen, Thomas F. Mikosch, Jochen Pietschnig, Rudolf Senftleben, Arne Chemical Physics 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.
title	Excited state assignment and state-resolved photoelectron circular dichroism in chalcogen-substituted fenchones
topic	Chemical Physics
url	https://arxiv.org/abs/2503.14261

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