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Bond dissociation energy and electronic spectroscopy of Cr + (NH 3 ) and its isotopomers

Journal Article · · Journal of Chemical Physics
DOI:https://doi.org/10.1063/1.5053691· OSTI ID:1543888
 [1];  [1];  [1]
  1. Univ. of Massachusetts, Amherst, MA (United States). Dept. of Chemistry
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The electronic spectra of Cr+(NH3), Cr+(ND3), and Cr+(15NH3) have been measured from 14 200 to 17 400 cm-1 using photodissociation spectroscopy. Transitions are predominantly observed from the 6A1 ground state, in which the Cr+ has a 3$$d$$5 electronic configuration, to the $$|tilde{B}$$ 6E ($$Π$$) state (3$$d$$44s). There is extensive vibronic structure in the spectrum due to a long progression in the Cr–N stretch and transitions to all six spin-orbit levels in the upper state. The spin-orbit splitting in the excited state is observed to be Aso$$'$$ = 39 cm-1. For the lowest spin-orbit level, the Cr–N stretching frequency in the excited state is 343 cm-1, with an anharmonicity of 4.2 cm-1. The 6E ($$Π$$) origin is predicted to lie at T0 = 14 697 cm-1. The first peak observed is due to v$$'$$ = 1, so the observed photodissociation onset is thermodynamic rather than spectroscopic, giving D0(Cr+-NH3) = 14 830 ± 100 cm-1 (177.4 ± 1.2 kJ/mol) and D0(Cr+–ND3) = 15 040 ± 30 cm-1 (179.9 ± 0.4 kJ/mol). The 6E ($$Π$$) state of Cr+(NH3) is ~2740 cm-1 less strongly bound than the ground state, and the Cr–N bond length increases by 0.23 ± 0.03 Å upon electronic excitation. Calculations at the time-dependent density functional theory (M06) and equations of motion coupled cluster, with single and double excitations (EOM-CCSD) level fairly accurately predict the energy and vibrational frequency of the excited state. Multi-reference configuration interaction calculations show how the spin-orbit states of Cr+(NH3) evolve into those of Cr+ + NH3.

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)
Grant/Contract Number:
AC02-05CH11231
OSTI ID:
1543888
Journal Information:
Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 17 Vol. 149; ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)Copyright Statement
Country of Publication:
United States
Language:
English

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