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Title: Low-lying vibronic level structure of the ground state of the methoxy radical: Slow electron velocity-map imaging (SEVI) spectra and Köppel-Domcke-Cederbaum (KDC) vibronic Hamiltonian calculations

Abstract

A joint experimental and theoretical study is reported on the low-lying vibronic level structure of the ground state of the methoxy radical using slow photoelectron velocity-map imaging spectroscopy of cryogenically cooled, mass-selected anions (cryo-SEVI) and Köppel-Domcke-Cederbaum (KDC) vibronic Hamiltonian calculations. The KDC vibronic model Hamiltonian in the present study was parametrized using high-level quantum chemistry, allowing the assignment of the cryo-SEVI spectra for vibronic levels of CH3O up to 2000 cm-1and of CD3O up to 1500 cm-1above the vibrational origin, using calculated vibronic wave functions. The adiabatic electron affinities of CH3O and CD3O are determined from the cryo-SEVI spectra to be 1.5689 ± 0.0007 eV and 1.5548 ± 0.0007 eV, respectively, demonstrating improved precision compared to previous work. Experimental peak splittings of <10 cm-1are resolved between the e1/2and e3/2components of the 61and 51vibronic levels. A pair of spin-vibronic levels at 1638 and 1677 cm-1were predicted in the calculation as the e1/2and e3/2components of 62levels and experimentally resolved for the first time. The strong variation of the spin-orbit splittings with a vibrational quantum number is in excellent agreement between theory and experiment. The observation of signals from nominally forbidden a1vibronic levels in the cryo-SEVI spectra also provides direct evidence of vibronicmore » coupling between ground and electronically excited states of methoxy.« less

Authors:
ORCiD logo [1]; ORCiD logo [2];  [3];  [4]; ORCiD logo [5]
+ Show Author Affiliations
  1. Univ. of California, Berkeley, CA (United States)
  2. The Johns Hopkins Univ., Baltimore, MD (United States)
  3. Univ. of California, Berkeley, CA (United States); SLAC National Accelerator Lab., Menlo Park, CA (United States)
  4. Univ. of Florida, Gainesville, FL (United States)
  5. Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Publication Date:
Research Org.:
SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1369391
Alternate Identifier(s):
OSTI ID: 1369081; OSTI ID: 1458498
Grant/Contract Number:  
AC02-76SF00515; CHE-1361031; AC02-05CH11231; FG02-07ER15884
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 146; Journal Issue: 22; 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

Weichman, Marissa L., Cheng, Lan, Kim, Jongjin B., Stanton, John F., and Neumark, Daniel M. Low-lying vibronic level structure of the ground state of the methoxy radical: Slow electron velocity-map imaging (SEVI) spectra and Köppel-Domcke-Cederbaum (KDC) vibronic Hamiltonian calculations. United States: N. p., 2017. Web. doi:10.1063/1.4984963.
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Weichman, Marissa L., Cheng, Lan, Kim, Jongjin B., Stanton, John F., & Neumark, Daniel M. Low-lying vibronic level structure of the ground state of the methoxy radical: Slow electron velocity-map imaging (SEVI) spectra and Köppel-Domcke-Cederbaum (KDC) vibronic Hamiltonian calculations. United States. https://doi.org/10.1063/1.4984963
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Weichman, Marissa L., Cheng, Lan, Kim, Jongjin B., Stanton, John F., and Neumark, Daniel M. Mon . "Low-lying vibronic level structure of the ground state of the methoxy radical: Slow electron velocity-map imaging (SEVI) spectra and Köppel-Domcke-Cederbaum (KDC) vibronic Hamiltonian calculations". United States. https://doi.org/10.1063/1.4984963. https://www.osti.gov/servlets/purl/1369391.
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@article{osti_1369391,
title = {Low-lying vibronic level structure of the ground state of the methoxy radical: Slow electron velocity-map imaging (SEVI) spectra and Köppel-Domcke-Cederbaum (KDC) vibronic Hamiltonian calculations},
author = {Weichman, Marissa L. and Cheng, Lan and Kim, Jongjin B. and Stanton, John F. and Neumark, Daniel M.},
abstractNote = {A joint experimental and theoretical study is reported on the low-lying vibronic level structure of the ground state of the methoxy radical using slow photoelectron velocity-map imaging spectroscopy of cryogenically cooled, mass-selected anions (cryo-SEVI) and Köppel-Domcke-Cederbaum (KDC) vibronic Hamiltonian calculations. The KDC vibronic model Hamiltonian in the present study was parametrized using high-level quantum chemistry, allowing the assignment of the cryo-SEVI spectra for vibronic levels of CH3O up to 2000 cm-1and of CD3O up to 1500 cm-1above the vibrational origin, using calculated vibronic wave functions. The adiabatic electron affinities of CH3O and CD3O are determined from the cryo-SEVI spectra to be 1.5689 ± 0.0007 eV and 1.5548 ± 0.0007 eV, respectively, demonstrating improved precision compared to previous work. Experimental peak splittings of <10 cm-1are resolved between the e1/2and e3/2components of the 61and 51vibronic levels. A pair of spin-vibronic levels at 1638 and 1677 cm-1were predicted in the calculation as the e1/2and e3/2components of 62levels and experimentally resolved for the first time. The strong variation of the spin-orbit splittings with a vibrational quantum number is in excellent agreement between theory and experiment. The observation of signals from nominally forbidden a1vibronic levels in the cryo-SEVI spectra also provides direct evidence of vibronic coupling between ground and electronically excited states of methoxy.},
doi = {10.1063/1.4984963},
journal = {Journal of Chemical Physics},
number = 22,
volume = 146,
place = {United States},
year = {Mon Jun 12 00:00:00 EDT 2017},
month = {Mon Jun 12 00:00:00 EDT 2017}
}
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    Works referencing / citing this record:

    Probing alkenoxy radical electronic structure using anion PEI spectroscopy
    journal, January 2019

    • Patros, Kellyn M.; Mann, Jennifer E.; Dobulis, Marissa A.
    • The Journal of Chemical Physics, Vol. 150, Issue 3
    • DOI: 10.1063/1.5064795

    Laser-induced fluorescence and dispersed-fluorescence spectroscopy of the Ã2E−X̃2A1 transition of jet-cooled calcium methoxide (CaOCH 3 ) radicals
    journal, October 2019

    • Paul, Anam C.; Sharma, Ketan; Reza, Md Asmaul
    • The Journal of Chemical Physics, Vol. 151, Issue 13
    • DOI: 10.1063/1.5104278
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