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Title: Probing cis-trans isomerization in the S1 state of C2H2 via H-atom action and hot band-pumped IR-UV double resonance spectroscopies

Abstract

We report novel experimental strategies that should prove instrumental in extending the vibrational and rotational assignments of the S1 state of acetylene, C2H2, in the region of the cis-trans isomerization barrier. At present, the assignments are essentially complete up to ~500 cm-1 below the barrier. Two difficulties arise when the assignments are continued to higher energies. One is that predissociation into C2H + H sets in roughly 1100 cm-1 below the barrier; the resulting quenching of laser-induced fluorescence (LIF) reduces its value for recording spectra in this region. The other difficulty is that tunneling through the barrier causes a staggering in the K-rotational structure of isomerizing vibrational levels. The assignment of these levels requires data for K values up to at least 3. Given the rotational selection rule K' - ℓ"= Å}1, such data must be obtained via excited vibrational levels of the ground state with ℓ" > 0. In this paper, high resolution H-atom resonance-enhanced multiphoton ionization spectra are demonstrated to contain predissociated bands which are almost invisible in LIF spectra, while preliminary data using a hyperthermal pulsed nozzle show that ℓ" = 2 states can be selectively populated in a jet, giving access to K' = 3 statesmore » in IR-UV double resonance.« less

Authors:
ORCiD logo [1]; ORCiD logo [1];  [2]; ORCiD logo [3]
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  1. Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States); Univ. of Colorado, Boulder, CO (United States)
  2. Academia Sinica, Taipei (Taiwan); Univ. of British Columbia, Vancouver, BC (Canada)
  3. Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)
Publication Date:
Research Org.:
Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); Academia Sinica; Natural Sciences and Engineering Research Council of Canada (NSERC)
OSTI Identifier:
1547032
Alternate Identifier(s):
OSTI ID: 1229645; OSTI ID: 1831805
Grant/Contract Number:  
FG02-87ER13671; FG0287ER13671
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 143; Journal Issue: 8; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
74 ATOMIC AND MOLECULAR PHYSICS

Citation Formats

Changala, P. Bryan, Baraban, Joshua H., Merer, Anthony J., and Field, Robert W. Probing cis-trans isomerization in the S1 state of C2H2 via H-atom action and hot band-pumped IR-UV double resonance spectroscopies. United States: N. p., 2015. Web. doi:10.1063/1.4929588.
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Changala, P. Bryan, Baraban, Joshua H., Merer, Anthony J., & Field, Robert W. Probing cis-trans isomerization in the S1 state of C2H2 via H-atom action and hot band-pumped IR-UV double resonance spectroscopies. United States. https://doi.org/10.1063/1.4929588
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Changala, P. Bryan, Baraban, Joshua H., Merer, Anthony J., and Field, Robert W. Thu . "Probing cis-trans isomerization in the S1 state of C2H2 via H-atom action and hot band-pumped IR-UV double resonance spectroscopies". United States. https://doi.org/10.1063/1.4929588. https://www.osti.gov/servlets/purl/1547032.
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@article{osti_1547032,
title = {Probing cis-trans isomerization in the S1 state of C2H2 via H-atom action and hot band-pumped IR-UV double resonance spectroscopies},
author = {Changala, P. Bryan and Baraban, Joshua H. and Merer, Anthony J. and Field, Robert W.},
abstractNote = {We report novel experimental strategies that should prove instrumental in extending the vibrational and rotational assignments of the S1 state of acetylene, C2H2, in the region of the cis-trans isomerization barrier. At present, the assignments are essentially complete up to ~500 cm-1 below the barrier. Two difficulties arise when the assignments are continued to higher energies. One is that predissociation into C2H + H sets in roughly 1100 cm-1 below the barrier; the resulting quenching of laser-induced fluorescence (LIF) reduces its value for recording spectra in this region. The other difficulty is that tunneling through the barrier causes a staggering in the K-rotational structure of isomerizing vibrational levels. The assignment of these levels requires data for K values up to at least 3. Given the rotational selection rule K' - ℓ"= Å}1, such data must be obtained via excited vibrational levels of the ground state with ℓ" > 0. In this paper, high resolution H-atom resonance-enhanced multiphoton ionization spectra are demonstrated to contain predissociated bands which are almost invisible in LIF spectra, while preliminary data using a hyperthermal pulsed nozzle show that ℓ" = 2 states can be selectively populated in a jet, giving access to K' = 3 states in IR-UV double resonance.},
doi = {10.1063/1.4929588},
journal = {Journal of Chemical Physics},
number = 8,
volume = 143,
place = {United States},
year = {Thu Aug 27 00:00:00 EDT 2015},
month = {Thu Aug 27 00:00:00 EDT 2015}
}
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https://doi.org/10.1063/1.4929588
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    Works referencing / citing this record:

    Hidden Dicarbene Nature of Acetylenes and Captodative Bonding on Carbon
    journal, October 2018

    • Bijina, Padinjare Veetil; Suresh, Cherumuttathu H.
    • ChemPhysChem, Vol. 19, Issue 23
    • DOI: 10.1002/cphc.201800726

    Photoinduced C–H bond fission in prototypical organic molecules and radicals
    journal, January 2019

    • Ashfold, Michael N. R.; Ingle, Rebecca A.; Karsili, Tolga N. V.
    • Physical Chemistry Chemical Physics, Vol. 21, Issue 26
    • DOI: 10.1039/c8cp07454b

    Probing the predissociated levels of the S 1 state of acetylene via H-atom fluorescence and photofragment fluorescence action spectroscopy
    journal, November 2018

    • Jiang, Jun; Saladrigas, Catherine A.; Erickson, Trevor J.
    • The Journal of Chemical Physics, Vol. 149, Issue 17
    • DOI: 10.1063/1.5045046
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