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

Abstract

The electronic spectra of Cr +(NH 3), Cr +(ND 3), and Cr +( 15NH 3) have been measured from 14 200 to 17 400 cm -1 using photodissociation spectroscopy. Transitions are predominantly observed from the 6A 1 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 A so$$'$$ = 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 T 0 = 14 697 cm -1. The first peak observed is due to v$$'$$ = 1, so the observed photodissociation onset is thermodynamic rather than spectroscopic, giving D 0(Cr +-NH 3) = 14 830 ± 100 cm -1 (177.4 ± 1.2 kJ/mol) and D 0(Cr +–ND 3) = 15 040 ± 30 cm -1 (179.9 ± 0.4 kJ/mol). The 6E ($$Π$$) state ofmore » Cr +(NH 3) 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 +(NH 3) evolve into those of Cr + + NH 3.« less

Authors:
 [1];  [1]; ORCiD logo [1]
  1. Univ. of Massachusetts, Amherst, MA (United States). Dept. of Chemistry
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:
1543888
Grant/Contract Number:  
AC02-05CH11231
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 149; Journal Issue: 17; 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; Chemistry; Physics

Citation Formats

Ashraf, Muhammad Affawn, Kozubal, Justine, and Metz, Ricardo B. Bond dissociation energy and electronic spectroscopy of Cr + (NH 3 ) and its isotopomers. United States: N. p., 2018. Web. doi:10.1063/1.5053691.
Ashraf, Muhammad Affawn, Kozubal, Justine, & Metz, Ricardo B. Bond dissociation energy and electronic spectroscopy of Cr + (NH 3 ) and its isotopomers. United States. https://doi.org/10.1063/1.5053691
Ashraf, Muhammad Affawn, Kozubal, Justine, and Metz, Ricardo B. Thu . "Bond dissociation energy and electronic spectroscopy of Cr + (NH 3 ) and its isotopomers". United States. https://doi.org/10.1063/1.5053691. https://www.osti.gov/servlets/purl/1543888.
@article{osti_1543888,
title = {Bond dissociation energy and electronic spectroscopy of Cr + (NH 3 ) and its isotopomers},
author = {Ashraf, Muhammad Affawn and Kozubal, Justine and Metz, Ricardo B.},
abstractNote = {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.},
doi = {10.1063/1.5053691},
url = {https://www.osti.gov/biblio/1543888}, journal = {Journal of Chemical Physics},
issn = {0021-9606},
number = 17,
volume = 149,
place = {United States},
year = {2018},
month = {11}
}

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