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Title: Uncovering Highly-Excited State Mixing in Acetone Using Ultrafast VUV Pulses and Coincidence Imaging Techniques

Abstract

Understanding the ultrafast dynamics of highly-excited electronic states of small molecules is critical for a better understanding of atmospheric and astrophysical processes, as well as for designing coherent control strategies for manipulating chemical dynamics. In highly excited states, nonadiabatic coupling, electron-electron interactions, and the high density of states govern dynamics. However, these states are computationally and experimentally challenging to access. Fortunately, new sources of ultrafast vacuum ultraviolet pulses, in combination with electron-ion coincidence spectroscopies, provide new tools to unravel the complex electronic landscape. Here we report time-resolved photoelectron-photoion coincidence experiments using 8 eV pump photons to study the highly excited states of acetone. We uncover for the first time direct evidence that the resulting excited state consists of a mixture of both $ηγ$→3$$ρ$$ and $$π$$→$$π$$* character, which decays with a time constant of 330 fs. In the future, this approach can inform models of VUV photochemistry and aid in designing coherent control strategies for manipulating chemical reactions.

Authors:
ORCiD logo [1];  [1];  [1];  [1]
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  1. Univ. of Colorado, Boulder, CO (United States)
Publication Date:
Research Org.:
Univ. of Colorado, Boulder, CO (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1348193
Alternate Identifier(s):
OSTI ID: 1686159
Grant/Contract Number:  
SC0012628; FG02-99ER14982; DGE-1650115
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory
Additional Journal Information:
Journal Volume: 121; Journal Issue: 12; Journal ID: ISSN 1089-5639
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 74 ATOMIC AND MOLECULAR PHYSICS; Ketones; Ionization; Cations; Excited states; Probes

Citation Formats

Couch, David E., Kapteyn, Henry C., Murnane, Margaret M., and Peters, William K. Uncovering Highly-Excited State Mixing in Acetone Using Ultrafast VUV Pulses and Coincidence Imaging Techniques. United States: N. p., 2017. Web. doi:10.1021/acs.jpca.7b01112.
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Couch, David E., Kapteyn, Henry C., Murnane, Margaret M., & Peters, William K. Uncovering Highly-Excited State Mixing in Acetone Using Ultrafast VUV Pulses and Coincidence Imaging Techniques. United States. https://doi.org/10.1021/acs.jpca.7b01112
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Couch, David E., Kapteyn, Henry C., Murnane, Margaret M., and Peters, William K. Tue . "Uncovering Highly-Excited State Mixing in Acetone Using Ultrafast VUV Pulses and Coincidence Imaging Techniques". United States. https://doi.org/10.1021/acs.jpca.7b01112. https://www.osti.gov/servlets/purl/1348193.
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@article{osti_1348193,
title = {Uncovering Highly-Excited State Mixing in Acetone Using Ultrafast VUV Pulses and Coincidence Imaging Techniques},
author = {Couch, David E. and Kapteyn, Henry C. and Murnane, Margaret M. and Peters, William K.},
abstractNote = {Understanding the ultrafast dynamics of highly-excited electronic states of small molecules is critical for a better understanding of atmospheric and astrophysical processes, as well as for designing coherent control strategies for manipulating chemical dynamics. In highly excited states, nonadiabatic coupling, electron-electron interactions, and the high density of states govern dynamics. However, these states are computationally and experimentally challenging to access. Fortunately, new sources of ultrafast vacuum ultraviolet pulses, in combination with electron-ion coincidence spectroscopies, provide new tools to unravel the complex electronic landscape. Here we report time-resolved photoelectron-photoion coincidence experiments using 8 eV pump photons to study the highly excited states of acetone. We uncover for the first time direct evidence that the resulting excited state consists of a mixture of both $ηγ$→3$ρ$ and $π$→$π$* character, which decays with a time constant of 330 fs. In the future, this approach can inform models of VUV photochemistry and aid in designing coherent control strategies for manipulating chemical reactions.},
doi = {10.1021/acs.jpca.7b01112},
journal = {Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory},
number = 12,
volume = 121,
place = {United States},
year = {Tue Mar 07 00:00:00 EST 2017},
month = {Tue Mar 07 00:00:00 EST 2017}
}
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Publisher's Version of Record
https://doi.org/10.1021/acs.jpca.7b01112
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