skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Photofragment Imaging, Spectroscopy, and Theory of MnO +

Abstract

Density functional and ab initio calculations, along with photodissociation spectroscopy and ion imaging of MnO+ from 21,300 to 33,900 cm–1, are used to probe the photodissociation dynamics and bond strength of the manganese oxide cation (MnO+). These studies confirm the theoretical ground state (5Π) and determine the spin–orbit constant (A′ = 14 cm–1) of the dominant optically accessible excited state (5Π) in the region. Photodissociation via this excited 5Π state results in ground state Mn+ (7S) + O (3P) products. At energies above 30,000 cm–1, the Mn+ (5S) + O (3P) channel is energetically accessible and becomes the preferred dissociation pathway. The bond dissociation energy (D0 = 242 ± 5 kJ/mol) of MnO+ is measured from several images of each photofragmentation channel and compared to theory, resolving a disagreement in previous measurements. MRCI+Q calculations are much more successful in predicting the observed spectrum than TD-DFT or EOM-CCSD calculations.

Authors:
 [1];  [1]; ORCiD logo [1]
  1. Department of Chemistry, University of Massachusetts Amherst, Amherst, Massachusetts 01003, United States
Publication Date:
Research Org.:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC); Univ. of California, Oakland, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1543637
DOE Contract Number:  
AC02-05CH11231
Resource Type:
Journal Article
Journal Name:
Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory
Additional Journal Information:
Journal Volume: 122; Journal Issue: 40; Journal ID: ISSN 1089-5639
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
Chemistry; Physics

Citation Formats

Johnston, M. David, Gentry, Matthew R., and Metz, Ricardo B. Photofragment Imaging, Spectroscopy, and Theory of MnO +. United States: N. p., 2018. Web. doi:10.1021/acs.jpca.8b07849.
Johnston, M. David, Gentry, Matthew R., & Metz, Ricardo B. Photofragment Imaging, Spectroscopy, and Theory of MnO +. United States. doi:10.1021/acs.jpca.8b07849.
Johnston, M. David, Gentry, Matthew R., and Metz, Ricardo B. Tue . "Photofragment Imaging, Spectroscopy, and Theory of MnO +". United States. doi:10.1021/acs.jpca.8b07849.
@article{osti_1543637,
title = {Photofragment Imaging, Spectroscopy, and Theory of MnO +},
author = {Johnston, M. David and Gentry, Matthew R. and Metz, Ricardo B.},
abstractNote = {Density functional and ab initio calculations, along with photodissociation spectroscopy and ion imaging of MnO+ from 21,300 to 33,900 cm–1, are used to probe the photodissociation dynamics and bond strength of the manganese oxide cation (MnO+). These studies confirm the theoretical ground state (5Π) and determine the spin–orbit constant (A′ = 14 cm–1) of the dominant optically accessible excited state (5Π) in the region. Photodissociation via this excited 5Π state results in ground state Mn+ (7S) + O (3P) products. At energies above 30,000 cm–1, the Mn+ (5S) + O (3P) channel is energetically accessible and becomes the preferred dissociation pathway. The bond dissociation energy (D0 = 242 ± 5 kJ/mol) of MnO+ is measured from several images of each photofragmentation channel and compared to theory, resolving a disagreement in previous measurements. MRCI+Q calculations are much more successful in predicting the observed spectrum than TD-DFT or EOM-CCSD calculations.},
doi = {10.1021/acs.jpca.8b07849},
journal = {Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory},
issn = {1089-5639},
number = 40,
volume = 122,
place = {United States},
year = {2018},
month = {9}
}