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Title: Infrared spectroscopy and tunneling dynamics of the vinyl radical in 4He nanodroplets

Abstract

Here, the vinyl radical has been trapped in 4He nanodroplets and probed with infrared laser spectroscopy in the CH stretch region between 2850 and 3200 cm -1. The assigned band origins for the CH 2 symmetric (ν 3), CH 2 antisymmetric (ν 2), and lone α-CH stretch (ν 1) vibrations are in good agreement with previously reported full-dimensional vibrational configuration interaction computations. For all three bands, a-type and b-type transitions are observed from the lowest symmetry allowed roconvibrational state of each nuclear spin isomer, which allows for a determination of the tunneling splittings in both the ground and excited vibrational levels. Comparisons to gas phase millimeter-wave rotation-tunneling and high-resolution jet-cooled infrared spectra reveal that the He solvent effect is to reduce the ground and ν 3 excited state tunneling splittings by ≈20%. This solvent-induced modification of the tunneling dynamics can be reasonably accounted for by assuming either a ≈2.5% increase in the effective barrier height along the tunneling coordinate or a ≈5% increase in the effective reduced mass of the tunneling particles.

Authors:
 [1];  [1]; ORCiD logo [1]
  1. Univ. of Georgia, Athens, GA (United States)
Publication Date:
Research Org.:
Univ. of Georgia Research Foundation, Athens, GA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division
OSTI Identifier:
1409045
Grant/Contract Number:  
SC0008086
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 138; Journal Issue: 17; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Raston, Paul L., Liang, Tao, and Douberly, Gary E. Infrared spectroscopy and tunneling dynamics of the vinyl radical in 4He nanodroplets. United States: N. p., 2013. Web. doi:10.1063/1.4802767.
Raston, Paul L., Liang, Tao, & Douberly, Gary E. Infrared spectroscopy and tunneling dynamics of the vinyl radical in 4He nanodroplets. United States. doi:10.1063/1.4802767.
Raston, Paul L., Liang, Tao, and Douberly, Gary E. Wed . "Infrared spectroscopy and tunneling dynamics of the vinyl radical in 4He nanodroplets". United States. doi:10.1063/1.4802767. https://www.osti.gov/servlets/purl/1409045.
@article{osti_1409045,
title = {Infrared spectroscopy and tunneling dynamics of the vinyl radical in 4He nanodroplets},
author = {Raston, Paul L. and Liang, Tao and Douberly, Gary E.},
abstractNote = {Here, the vinyl radical has been trapped in 4He nanodroplets and probed with infrared laser spectroscopy in the CH stretch region between 2850 and 3200 cm-1. The assigned band origins for the CH2 symmetric (ν3), CH2 antisymmetric (ν2), and lone α-CH stretch (ν1) vibrations are in good agreement with previously reported full-dimensional vibrational configuration interaction computations. For all three bands, a-type and b-type transitions are observed from the lowest symmetry allowed roconvibrational state of each nuclear spin isomer, which allows for a determination of the tunneling splittings in both the ground and excited vibrational levels. Comparisons to gas phase millimeter-wave rotation-tunneling and high-resolution jet-cooled infrared spectra reveal that the He solvent effect is to reduce the ground and ν3 excited state tunneling splittings by ≈20%. This solvent-induced modification of the tunneling dynamics can be reasonably accounted for by assuming either a ≈2.5% increase in the effective barrier height along the tunneling coordinate or a ≈5% increase in the effective reduced mass of the tunneling particles.},
doi = {10.1063/1.4802767},
journal = {Journal of Chemical Physics},
number = 17,
volume = 138,
place = {United States},
year = {2013},
month = {5}
}

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