Photofragment Imaging, Spectroscopy, and Theory of MnO +
- Department of Chemistry, University of Massachusetts Amherst, Amherst, Massachusetts 01003, United States
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.
- Research Organization:
- Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC); Univ. of California, Oakland, CA (United States)
- Sponsoring Organization:
- USDOE Office of Science (SC)
- DOE Contract Number:
- AC02-05CH11231
- OSTI ID:
- 1543637
- Journal Information:
- Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory, Journal Name: Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory Journal Issue: 40 Vol. 122; ISSN 1089-5639
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
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