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

Couch, David E.; Kapteyn, Henry C.; Murnane, Margaret M.; Peters, William K.

doi:10.1021/acs.jpca.7b01112

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

Journal Article · Tue Mar 07 00:00:00 EST 2017 · Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory

DOI:https://doi.org/10.1021/acs.jpca.7b01112· OSTI ID:1348193

^[1]; Kapteyn, Henry C. ^[2]; Murnane, Margaret M. ^[2]; Peters, William K. ^[2]

Univ. of Colorado, Boulder, CO (United States); JILA, University of Colorado at Boulder
Univ. of Colorado, Boulder, CO (United States)

Here, 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 n_y → 3p 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.

View Accepted Manuscript (DOE)

Research Organization:: Univ. of Colorado, Boulder, CO (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: FG02-99ER14982; SC0012628

OSTI ID:: 1348193

Alternate ID(s):: OSTI ID: 1686159

Journal Information:: Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory, Journal Name: Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory Journal Issue: 12 Vol. 121; ISSN 1089-5639

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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