Infrared spectroscopy and tunneling dynamics of the vinyl radical in 4He nanodroplets

Raston, Paul L.; Liang, Tao; Douberly, Gary E.

doi:10.1063/1.4802767

Infrared spectroscopy and tunneling dynamics of the vinyl radical in ⁴He nanodroplets

Journal Article · Wed May 01 04:00:00 EDT 2013 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.4802767· OSTI ID:1409045

Raston, Paul L. ^[1]; Liang, Tao ^[2]; ^[2]

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

Here, the vinyl radical has been trapped in ⁴He nanodroplets and probed with infrared laser spectroscopy in the CH stretch region between 2850 and 3200 cm^-1. The assigned band origins for the CH₂ symmetric (ν₃), CH₂ antisymmetric (ν₂), and lone α-CH stretch (ν₁) vibrations are in good agreement with previously reported full-dimensional vibrational configuration interaction computations. For all three bands, a-type and b-type transitions are observed from the lowest symmetry allowed roconvibrational state of each nuclear spin isomer, which allows for a determination of the tunneling splittings in both the ground and excited vibrational levels. Comparisons to gas phase millimeter-wave rotation-tunneling and high-resolution jet-cooled infrared spectra reveal that the He solvent effect is to reduce the ground and ν₃ excited state tunneling splittings by ≈20%. This solvent-induced modification of the tunneling dynamics can be reasonably accounted for by assuming either a ≈2.5% increase in the effective barrier height along the tunneling coordinate or a ≈5% increase in the effective reduced mass of the tunneling particles.

View Accepted Manuscript (DOE)

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

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division

Grant/Contract Number:: SC0008086

OSTI ID:: 1409045

Journal Information:: Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 17 Vol. 138; ISSN 0021-9606

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

Country of Publication:: United States

Language:: English

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Cited By (2)

Rovibrational quantum dynamics of the vinyl radical and its deuterated isotopologues Šmydke, Jan; Fábri, Csaba; Sarka, János Physical Chemistry Chemical Physics, Vol. 21, Issue 7 https://doi.org/10.1039/c8cp04672g	journal	January 2019
A rigorous full-dimensional quantum dynamics study of tunneling splitting of rovibrational states of vinyl radical C ₂ H ₃ Yu, Hua-Gen; Song, Hongwei; Yang, Minghui The Journal of Chemical Physics, Vol. 146, Issue 22 https://doi.org/10.1063/1.4985183	journal	June 2017

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