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Title: Reinterpretation of the electronic absorption spectrum of the methylene amidogen radical (H 2CN)

Abstract

The odd electronic absorption spectrum of H 2CN has been of great interest to experiment. Herein, this system is reported on extensively by applying theoretical methods to the ground and low-lying excited electronic states. Employing a large breadth of high-level ab initio computations, including coupled cluster [CCSD(T) and CCSDT(Q)] and multireference configuration interaction [MRCISD+Q] methods, we comprehensively demonstrate that the most recent experimental and theoretical interpretations of the electronic spectrum of H 2CN are in error. The previous assignments of the two broad features in the spectrum as the origin 0$$^{0}_{0}$$ (~35 050 cm –1) and 4$$^{2}_{0}$$ (~35 600 cm –1)$$\widetilde{B}$$ 2A 1←$$\widetilde{X}$$ 2B 2 transitions are both found to be incorrect. The presently reported transition energies suggest that the higher energy band near 35 600 cm –1 is the true origin band. Moreover, from the computed anharmonic vibrational frequencies of the $$\widetilde{X}$$ 2B 2 and $$\widetilde{B}$$ 2A 1 states, we demonstrate that this ~550 cm –1 band spacing cannot be attributed to a simple vibronic transition, as claimed by the 4$$^{2}_{0}$$ assignment. Possible alternative explanations for the appearance of the lower intensity band near 35 050 cm –1 are discussed.

Authors:
ORCiD logo [1];  [1];  [1]
  1. Univ. of Georgia, Athens, GA (United States)
Publication Date:
Research Org.:
Univ. of Georgia, Athens, GA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1540243
Alternate Identifier(s):
OSTI ID: 1468875
Grant/Contract Number:  
[SC0015512]
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
[ Journal Volume: 149; Journal Issue: 9]; 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

Citation Formats

Abbott, Adam S., Glick, Zach L., and Schaefer, Henry F. Reinterpretation of the electronic absorption spectrum of the methylene amidogen radical (H2CN). United States: N. p., 2018. Web. doi:10.1063/1.5042763.
Abbott, Adam S., Glick, Zach L., & Schaefer, Henry F. Reinterpretation of the electronic absorption spectrum of the methylene amidogen radical (H2CN). United States. doi:10.1063/1.5042763.
Abbott, Adam S., Glick, Zach L., and Schaefer, Henry F. Thu . "Reinterpretation of the electronic absorption spectrum of the methylene amidogen radical (H2CN)". United States. doi:10.1063/1.5042763. https://www.osti.gov/servlets/purl/1540243.
@article{osti_1540243,
title = {Reinterpretation of the electronic absorption spectrum of the methylene amidogen radical (H2CN)},
author = {Abbott, Adam S. and Glick, Zach L. and Schaefer, Henry F.},
abstractNote = {The odd electronic absorption spectrum of H2CN has been of great interest to experiment. Herein, this system is reported on extensively by applying theoretical methods to the ground and low-lying excited electronic states. Employing a large breadth of high-level ab initio computations, including coupled cluster [CCSD(T) and CCSDT(Q)] and multireference configuration interaction [MRCISD+Q] methods, we comprehensively demonstrate that the most recent experimental and theoretical interpretations of the electronic spectrum of H2CN are in error. The previous assignments of the two broad features in the spectrum as the origin 0$^{0}_{0}$ (~35 050 cm–1) and 4$^{2}_{0}$ (~35 600 cm–1)$\widetilde{B}$2A1←$\widetilde{X}$2B2 transitions are both found to be incorrect. The presently reported transition energies suggest that the higher energy band near 35 600 cm–1 is the true origin band. Moreover, from the computed anharmonic vibrational frequencies of the $\widetilde{X}$2B2 and $\widetilde{B}$2A1 states, we demonstrate that this ~550 cm–1 band spacing cannot be attributed to a simple vibronic transition, as claimed by the 4$^{2}_{0}$ assignment. Possible alternative explanations for the appearance of the lower intensity band near 35 050 cm–1 are discussed.},
doi = {10.1063/1.5042763},
journal = {Journal of Chemical Physics},
number = [9],
volume = [149],
place = {United States},
year = {2018},
month = {9}
}

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