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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

Journal Article · · Journal of Chemical Physics
DOI:https://doi.org/10.1063/1.4984963· OSTI ID:1369391
 [1];  [2];  [3];  [4];  [5]
  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)
+ Show Author Affiliations
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–1 and of CD3O up to 1500 cm–1 above 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–1 are resolved between the e1/2 and e3/2 components of the 61 and 51 vibronic levels. A pair of spin-vibronic levels at 1638 and 1677 cm–1 were predicted in the calculation as the e1/2 and e3/2 components of 62 levels 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. In conclusion, the observation of signals from nominally forbidden a1 vibronic levels in the cryo-SEVI spectra also provides direct evidence of vibronic coupling between ground and electronically excited states of methoxy.
Research Organization:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States); SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)
Sponsoring Organization:
USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Grant/Contract Number:
AC02-05CH11231; AC02-76SF00515; FG02-07ER15884
OSTI ID:
1369391
Alternate ID(s):
OSTI ID: 1369081
OSTI ID: 1458498
Journal Information:
Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 22 Vol. 146; ISSN JCPSA6; ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)Copyright Statement
Country of Publication:
United States
Language:
English

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Cited By (2)

Probing alkenoxy radical electronic structure using anion PEI spectroscopy journal January 2019
Laser-induced fluorescence and dispersed-fluorescence spectroscopy of the Ã2E−X̃2A1 transition of jet-cooled calcium methoxide (CaOCH 3 ) radicals journal October 2019

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