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Title: A rigorous full-dimensional quantum dynamics study of tunneling splitting of rovibrational states of vinyl radical C 2 H 3

Journal Article · · Journal of Chemical Physics
DOI:https://doi.org/10.1063/1.4985183· OSTI ID:1366346
ORCiD logo [1];  [2];  [2]
  1. Brookhaven National Lab. (BNL), Upton, NY (United States). Dept. of Energy and Photon Sciences
  2. Chinese Academy of Sciences (CAS), Wuhan (China). State Key Lab. of Magnetic Resonance, Atomic and Molecular Physics, Wuhan Inst. of Physics and Mathematics
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Here, we report a rigorous quantum mechanical study of the rovibrational energy levels of vinyl radical C2H3. The calculations are carried out using a real two-component multi-layer Lanczos algorithm in a set of orthogonal polyspherical coordinates based on a recently developed accurate ab initio potential energy surface of C2H3. All well converged 158 vibrational bands up to 3200 cm-1 are determined, together with a comparison to previous calculations and experimental results. Our results show a remarkable multi-dimensional tunneling effect on the vibrational spectra of the radical. The vibrational tunneling splitting is substantially different from that of previous reduced dimensional calculations. The rotational constants of the fundamental vibrational bands of C2H3 are also given. It was found that the rovibrational states are strongly coupled, especially among those bending vibrational modes. Additionally, the perturbative iteration approach of Gruebele has been extended to assign the rovibrational energy levels of C2H3 without the requirement of explicit wavefunctions.

Research Organization:
Brookhaven National Laboratory (BNL), Upton, NY (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
SC00112704; AC0205CH11231
OSTI ID:
1366346
Alternate ID(s):
OSTI ID: 1363704
Report Number(s):
BNL-113978-2017-JA; R&D Project: CO006; KC0301020
Journal Information:
Journal of Chemical Physics, Vol. 146, Issue 22; ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)Copyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 16 works
Citation information provided by
Web of Science

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Cited By (4)

Computational study of the ro-vibrational spectrum of CO–CO 2 journal August 2019
On the use of reduced-density matrices for the semi-automatic assignment of vibrational states journal February 2019
Rovibrational quantum dynamics of the vinyl radical and its deuterated isotopologues journal January 2019
The ionization energy of the vinyl radical: a Mexican standoff with a happy ending journal January 2019

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY