Millimeter-wave spectroscopy of HDC=CH

Masato Hayashi, Hiromu Matsubayashi, Tomohiro Ichiyama, Kensuke Harada, Keiichi Tanaka

Research output: Contribution to journalArticle

Abstract

Rotational transitions of the mono(β)-deuterated vinyl radical, HDC=CH, produced in a supersonic jet expansion by the ArF excimer laser photolysis, were observed by millimeter-wave spectroscopy. The b-type rotational transitions together with the weak a-type transitions were observed only for the lower component of the tunneling doublet, and no tunneling-rotation transitions connecting the lower and upper components were observed, suggesting that state mixing between the two components is negligibly small. The derived molecular constants such as the A rotational constant, Fermi contact interaction constants, and magnetic dipolar interaction constants indicate that the carrier of the observed spectrum is the trans-form of HDC=CH isomers, where the α-proton is located on the opposite side of the β-deuteron. The present conclusion of the trans-form of HDC=CH was also supported by the ab initio calculation in the CCSD(T)/cc-pVTZ level since the trans-form is calculated to be located by 30.04 cm-1 lower than the cis-form due to the difference in the zero point energy. As a result, the tunneling components in the ground state of HDC=CH behave as two different isomers localized at the trans- and cis-wells of the asymmetric double minimum potential. Observed hyperfine constants for HDC=CH were compared with those for H2C=CH to be consistent with each other.

Original languageEnglish
Article number184304
JournalJournal of Chemical Physics
Volume151
Issue number18
DOIs
Publication statusPublished - Nov 14 2019

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Millimeter waves
Isomers
millimeter waves
Spectroscopy
methylidyne
Deuterium
Photolysis
Excimer lasers
Ground state
spectroscopy
Protons
isomers
vinyl radical
zero point energy
excimer lasers
deuterons
photolysis
electric contacts
interactions
expansion

All Science Journal Classification (ASJC) codes

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

Cite this

Hayashi, M., Matsubayashi, H., Ichiyama, T., Harada, K., & Tanaka, K. (2019). Millimeter-wave spectroscopy of HDC=CH. Journal of Chemical Physics, 151(18), [184304]. https://doi.org/10.1063/1.5126671

Millimeter-wave spectroscopy of HDC=CH. / Hayashi, Masato; Matsubayashi, Hiromu; Ichiyama, Tomohiro; Harada, Kensuke; Tanaka, Keiichi.

In: Journal of Chemical Physics, Vol. 151, No. 18, 184304, 14.11.2019.

Research output: Contribution to journalArticle

Hayashi, M, Matsubayashi, H, Ichiyama, T, Harada, K & Tanaka, K 2019, 'Millimeter-wave spectroscopy of HDC=CH', Journal of Chemical Physics, vol. 151, no. 18, 184304. https://doi.org/10.1063/1.5126671
Hayashi M, Matsubayashi H, Ichiyama T, Harada K, Tanaka K. Millimeter-wave spectroscopy of HDC=CH. Journal of Chemical Physics. 2019 Nov 14;151(18). 184304. https://doi.org/10.1063/1.5126671
Hayashi, Masato ; Matsubayashi, Hiromu ; Ichiyama, Tomohiro ; Harada, Kensuke ; Tanaka, Keiichi. / Millimeter-wave spectroscopy of HDC=CH. In: Journal of Chemical Physics. 2019 ; Vol. 151, No. 18.
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