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Title: Infrared Stark and Zeeman spectroscopy of OH–CO: The entrance channel complex along the OH + CO → trans-HOCO reaction pathway

Abstract

Here, sequential capture of OH and CO by superfluid helium droplets leads exclusively to the formation of the linear, entrance-channel complex, OH-CO. This species is characterized by infrared laser Stark and Zeeman spectroscopy via measurements of the fundamental OH stretching vibration. Experimental dipole moments are in disagreement with ab initio calculations at the equilibrium geometry, indicating large-amplitude motion on the ground state potential energy surface. Vibrational averaging along the hydroxyl bending coordinate recovers 80% of the observed deviation from the equilibrium dipole moment. Inhomogeneous line broadening in the zero-field spectrum is modeled with an effective Hamiltonian approach that aims to account for the anisotropic molecule-helium interaction potential that arises as the OH-CO complex is displaced from the center of the droplet.

Authors:
 [1];  [1]; ORCiD logo [2];  [3]; ORCiD logo [1]
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  1. Univ. of Georgia, Athens, GA (United States)
  2. James Madison Univ., Harrisonburg, VA (United States)
  3. Univ. of Washington, Seattle, WA (United States)
Publication Date:
Research Org.:
Univ. of Georgia, Athens, GA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division
OSTI Identifier:
1409062
Alternate Identifier(s):
OSTI ID: 1328586
Grant/Contract Number:  
SC0008086; FG02-12ER16298
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 145; Journal Issue: 12; 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

Brice, Joseph T., Liang, Tao, Raston, Paul L., McCoy, Anne B., and Douberly, Gary E. Infrared Stark and Zeeman spectroscopy of OH–CO: The entrance channel complex along the OH + CO → trans-HOCO reaction pathway. United States: N. p., 2016. Web. doi:10.1063/1.4963226.
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Brice, Joseph T., Liang, Tao, Raston, Paul L., McCoy, Anne B., & Douberly, Gary E. Infrared Stark and Zeeman spectroscopy of OH–CO: The entrance channel complex along the OH + CO → trans-HOCO reaction pathway. United States. https://doi.org/10.1063/1.4963226
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Brice, Joseph T., Liang, Tao, Raston, Paul L., McCoy, Anne B., and Douberly, Gary E. Tue . "Infrared Stark and Zeeman spectroscopy of OH–CO: The entrance channel complex along the OH + CO → trans-HOCO reaction pathway". United States. https://doi.org/10.1063/1.4963226. https://www.osti.gov/servlets/purl/1409062.
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@article{osti_1409062,
title = {Infrared Stark and Zeeman spectroscopy of OH–CO: The entrance channel complex along the OH + CO → trans-HOCO reaction pathway},
author = {Brice, Joseph T. and Liang, Tao and Raston, Paul L. and McCoy, Anne B. and Douberly, Gary E.},
abstractNote = {Here, sequential capture of OH and CO by superfluid helium droplets leads exclusively to the formation of the linear, entrance-channel complex, OH-CO. This species is characterized by infrared laser Stark and Zeeman spectroscopy via measurements of the fundamental OH stretching vibration. Experimental dipole moments are in disagreement with ab initio calculations at the equilibrium geometry, indicating large-amplitude motion on the ground state potential energy surface. Vibrational averaging along the hydroxyl bending coordinate recovers 80% of the observed deviation from the equilibrium dipole moment. Inhomogeneous line broadening in the zero-field spectrum is modeled with an effective Hamiltonian approach that aims to account for the anisotropic molecule-helium interaction potential that arises as the OH-CO complex is displaced from the center of the droplet.},
doi = {10.1063/1.4963226},
journal = {Journal of Chemical Physics},
number = 12,
volume = 145,
place = {United States},
year = {Tue Sep 27 00:00:00 EDT 2016},
month = {Tue Sep 27 00:00:00 EDT 2016}
}
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https://doi.org/10.1063/1.4963226
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