Cargando…

Pump-probe spectroscopy of chiral vibrational dynamics

A planar molecule may become chiral upon excitation of an out-of-plane vibration, changing its handedness during half a vibrational period. When exciting such a vibration in an ensemble of randomly oriented molecules with an infrared laser, half of the molecules will undergo the vibration phase-shif...

Descripción completa

Detalles Bibliográficos
Autores principales: Tikhonov, Denis S., Blech, Alexander, Leibscher, Monika, Greenman, Loren, Schnell, Melanie, Koch, Christiane P.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Association for the Advancement of Science 2022
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9728962/
https://www.ncbi.nlm.nih.gov/pubmed/36475788
http://dx.doi.org/10.1126/sciadv.ade0311
_version_ 1784845385057959936
author Tikhonov, Denis S.
Blech, Alexander
Leibscher, Monika
Greenman, Loren
Schnell, Melanie
Koch, Christiane P.
author_facet Tikhonov, Denis S.
Blech, Alexander
Leibscher, Monika
Greenman, Loren
Schnell, Melanie
Koch, Christiane P.
author_sort Tikhonov, Denis S.
collection PubMed
description A planar molecule may become chiral upon excitation of an out-of-plane vibration, changing its handedness during half a vibrational period. When exciting such a vibration in an ensemble of randomly oriented molecules with an infrared laser, half of the molecules will undergo the vibration phase-shifted by π compared to the other half, and no net chiral signal is observed. This symmetry can be broken by exciting the vibrational motion with a Raman transition in the presence of a static electric field. Subsequent ionization of the vibrating molecules by an extreme ultraviolet pulse probes the time-dependent net handedness via the photoelectron circular dichroism. Our proposal for pump-probe spectroscopy of molecular chirality, based on quantum-chemical theory and discussed for the example of the carbonyl chlorofluoride molecule, is feasible with current experimental technology.
format Online
Article
Text
id pubmed-9728962
institution National Center for Biotechnology Information
language English
publishDate 2022
publisher American Association for the Advancement of Science
record_format MEDLINE/PubMed
spelling pubmed-97289622022-12-13 Pump-probe spectroscopy of chiral vibrational dynamics Tikhonov, Denis S. Blech, Alexander Leibscher, Monika Greenman, Loren Schnell, Melanie Koch, Christiane P. Sci Adv Physical and Materials Sciences A planar molecule may become chiral upon excitation of an out-of-plane vibration, changing its handedness during half a vibrational period. When exciting such a vibration in an ensemble of randomly oriented molecules with an infrared laser, half of the molecules will undergo the vibration phase-shifted by π compared to the other half, and no net chiral signal is observed. This symmetry can be broken by exciting the vibrational motion with a Raman transition in the presence of a static electric field. Subsequent ionization of the vibrating molecules by an extreme ultraviolet pulse probes the time-dependent net handedness via the photoelectron circular dichroism. Our proposal for pump-probe spectroscopy of molecular chirality, based on quantum-chemical theory and discussed for the example of the carbonyl chlorofluoride molecule, is feasible with current experimental technology. American Association for the Advancement of Science 2022-12-07 /pmc/articles/PMC9728962/ /pubmed/36475788 http://dx.doi.org/10.1126/sciadv.ade0311 Text en Copyright © 2022 The Authors, some rights reserved; exclusive licensee American Association for the Advancement of Science. No claim to original U.S. Government Works. Distributed under a Creative Commons Attribution License 4.0 (CC BY). https://creativecommons.org/licenses/by/4.0/This is an open-access article distributed under the terms of the Creative Commons Attribution license (https://creativecommons.org/licenses/by/4.0/) , which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.
spellingShingle Physical and Materials Sciences
Tikhonov, Denis S.
Blech, Alexander
Leibscher, Monika
Greenman, Loren
Schnell, Melanie
Koch, Christiane P.
Pump-probe spectroscopy of chiral vibrational dynamics
title Pump-probe spectroscopy of chiral vibrational dynamics
title_full Pump-probe spectroscopy of chiral vibrational dynamics
title_fullStr Pump-probe spectroscopy of chiral vibrational dynamics
title_full_unstemmed Pump-probe spectroscopy of chiral vibrational dynamics
title_short Pump-probe spectroscopy of chiral vibrational dynamics
title_sort pump-probe spectroscopy of chiral vibrational dynamics
topic Physical and Materials Sciences
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9728962/
https://www.ncbi.nlm.nih.gov/pubmed/36475788
http://dx.doi.org/10.1126/sciadv.ade0311
work_keys_str_mv AT tikhonovdeniss pumpprobespectroscopyofchiralvibrationaldynamics
AT blechalexander pumpprobespectroscopyofchiralvibrationaldynamics
AT leibschermonika pumpprobespectroscopyofchiralvibrationaldynamics
AT greenmanloren pumpprobespectroscopyofchiralvibrationaldynamics
AT schnellmelanie pumpprobespectroscopyofchiralvibrationaldynamics
AT kochchristianep pumpprobespectroscopyofchiralvibrationaldynamics