Reinterpretation of the electronic absorption spectrum of the methylene amidogen radical (H2CN)

Abbott, Adam S.; Glick, Zach L.; Schaefer, Henry F.

doi:10.1063/1.5042763

Title: Reinterpretation of the electronic absorption spectrum of the methylene amidogen radical (H₂CN)

Journal Article · Thu Sep 06 00:00:00 EDT 2018 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.5042763· OSTI ID:1540243

^[1]; Glick, Zach L. ^[1]; Schaefer, Henry F. ^[1]

Univ. of Georgia, Athens, GA (United States)

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.

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Research Organization:: Univ. of Georgia, Athens, GA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0015512

OSTI ID:: 1540243

Alternate ID(s):: OSTI ID: 1468875

Journal Information:: Journal of Chemical Physics, Vol. 149, Issue 9; ISSN 0021-9606

Publisher:: American Institute of Physics (AIP)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 1 work

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