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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

Abstract

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.

Authors:
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
Publication Date:
Research Org.:
Brookhaven National Lab. (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1366346
Alternate Identifier(s):
OSTI ID: 1363704
Report Number(s):
BNL-113978-2017-JA
Journal ID: ISSN 0021-9606; R&D Project: CO006; KC0301020
Grant/Contract Number:  
SC00112704; AC0205CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 146; Journal Issue: 22; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Yu, Hua-Gen, Song, Hongwei, and Yang, Minghui. A rigorous full-dimensional quantum dynamics study of tunneling splitting of rovibrational states of vinyl radical C 2 H 3. United States: N. p., 2017. Web. doi:10.1063/1.4985183.
Yu, Hua-Gen, Song, Hongwei, & Yang, Minghui. A rigorous full-dimensional quantum dynamics study of tunneling splitting of rovibrational states of vinyl radical C 2 H 3. United States. doi:10.1063/1.4985183.
Yu, Hua-Gen, Song, Hongwei, and Yang, Minghui. Mon . "A rigorous full-dimensional quantum dynamics study of tunneling splitting of rovibrational states of vinyl radical C 2 H 3". United States. doi:10.1063/1.4985183. https://www.osti.gov/servlets/purl/1366346.
@article{osti_1366346,
title = {A rigorous full-dimensional quantum dynamics study of tunneling splitting of rovibrational states of vinyl radical C 2 H 3},
author = {Yu, Hua-Gen and Song, Hongwei and Yang, Minghui},
abstractNote = {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.},
doi = {10.1063/1.4985183},
journal = {Journal of Chemical Physics},
number = 22,
volume = 146,
place = {United States},
year = {2017},
month = {6}
}

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