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

All Science Journal Classification (ASJC) codes

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

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    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