Rovibrational quantum dynamics of the vinyl radical and its deuterated isotopologues

Jan Šmydke, Csaba Fábri, János Sarka, A. Császár

Research output: Contribution to journalArticle

2 Citations (Scopus)

Abstract

Rotational-vibrational states up to 3200 cm -1 , beyond the highest-lying stretching fundamental, are computed variationally for the vinyl radical (VR), H 2 C β C α H, and the following deuterated isotopologues of VR: CH 2 CD, CHDCH, and CD 2 CD. The height of the C α H tunneling rocking barrier of VR, partially responsible for the complex nuclear dynamics of VR and its isotopologues, is determined to be 1641 ± 25 cm -1 by the focal-point analysis approach. The definitive nuclear-motion computations performed utilize two previously published potential energy hypersurfaces and reveal interesting energy-level and tunneling patterns characterizing the internal motions of the four isotopologues. A full assignment, including symmetry labels, of the vibrational states computed for CH 2 CH is provided, whenever feasible, based on the analysis of wave functions and the related one- and two-mode reduced density matrices. The computed vibrational states of CH 2 CD and CD 2 CD are characterized up to slightly above the top of the barrier. Interestingly, it is the interplay of the ν 6 (formally CH 2 rock) and ν 7 (formally CH rock) modes that determines the tunneling dynamics; thus, the description of tunneling in VR needs, as a minimum, the consideration of two in-plane bending motions at the two ends of the molecule. When feasible, the computed results are compared to their experimental counterparts as well as to previous computational results. Corrections to the placement of the ν 4 and ν 6 fundamentals of VR are proposed. Tunneling switching, a unique phenomenon characterizing tunneling in slightly asymmetric effective double-well potentials, is observed and discussed for CHDCH. Despite the extensive tunneling dynamics, the rotational energy-level structure of VR exhibits rigid-rotor-type behavior.

Original languageEnglish
Pages (from-to)3453-3472
Number of pages20
JournalPhysical Chemistry Chemical Physics
Volume21
Issue number7
DOIs
Publication statusPublished - Jan 1 2019

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vinyl radical
Electron energy levels
methylidyne
Rigid rotors
vibrational states
Wave functions
Potential energy
Stretching
Labels
Rocks
energy levels
Molecules
rigid rotors
potential energy
wave functions
rocks
symmetry

ASJC Scopus subject areas

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

Cite this

Rovibrational quantum dynamics of the vinyl radical and its deuterated isotopologues. / Šmydke, Jan; Fábri, Csaba; Sarka, János; Császár, A.

In: Physical Chemistry Chemical Physics, Vol. 21, No. 7, 01.01.2019, p. 3453-3472.

Research output: Contribution to journalArticle

Šmydke, Jan ; Fábri, Csaba ; Sarka, János ; Császár, A. / Rovibrational quantum dynamics of the vinyl radical and its deuterated isotopologues. In: Physical Chemistry Chemical Physics. 2019 ; Vol. 21, No. 7. pp. 3453-3472.
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