Skip to main content
OSTI.GOVU.S. Department of Energy Office of Scientific and Technical Information
U.S. Department of Energy
Office of Scientific and Technical Information
 

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
 [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
+ Show Author Affiliations
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; USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Grant/Contract Number:
AC02-05CH11231
OSTI ID:
1366346
Alternate ID(s):
OSTI ID: 1363704
Report Number(s):
BNL--113978-2017-JA; KC0301020
Journal Information:
Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 22 Vol. 146; ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)Copyright Statement
Country of Publication:
United States
Language:
English

References (63)

Multidimensional Quantum Dynamics book April 2009
Coupled channel methods for solving the bound-state Schrödinger equation journal November 1994
A modified potential energy surface for the C2H+H2↔C2H2+H reaction and a theoretical study on its rate constants journal June 2005
Exact and constrained kinetic energy operators for polyatomic molecules: The polyspherical approach journal November 2008
A general rigorous quantum dynamics algorithm to calculate vibrational energy levels of pentaatomic molecules journal August 2009
Exact and constrained kinetic energy operators for polyatomic molecules: The polyspherical approach journal November 2009
A low-storage filter-diagonalization method to calculate expectation values of operators non-commutative with the Hamiltonian: Vibrational assignment of HOCl journal July 1999
Quasi-Bound States of the F·CH 4 Complex journal January 2016
Ab Initio, Embedded Local-Monomer Calculations of Methane Vibrational Energies in Clathrate Hydrates journal February 2016
CH 5 + : Symmetry and the Entangled Rovibrational Quantum States of a Fluxional Molecule journal October 2015
Multidimensional Tunneling, Recrossing, and the Transmission Coefficient for Enzymatic Reactions journal August 2006
Theoretical study of the ethenyl radical in the electronic ground and excited states journal June 1985
Ab initio studies of (1,2)-hydrogen migrations in open-shell hydrocarbons: vinyl radical, ethyl radical, and triplet methylcarbene journal December 1981
Tunneling Splitting of Energy Levels and Rotational Constants in the Vinyl Radical C 2 H 3 † journal April 2006
Vibrational Modes of the Vinyl and Deuterated Vinyl Radicals journal August 2009
Ab initio large-amplitude quantum-tunneling dynamics in vinyl radical: a vibrationally adiabatic approach journal January 2008
Validation of the DFT/N07D computational model on the magnetic, vibrational and electronic properties of vinyl radical journal January 2010
The fourth age of quantum chemistry: molecules in motion journal January 2012
Neural network iterative diagonalization method to solve eigenvalue problems in quantum mechanics journal January 2015
Rovibrational transitions of the methane–water dimer from intermolecular quantum dynamical computations journal January 2016
Theoretical study of kinetic isotope effects on rate constants for the H2+C2H→H+C2H2 reaction and its isotopic variants journal September 2000
The Jacobi–Wilson method: A new approach to the description of polyatomic molecules journal February 2001
Electronic spectroscopy of jet-cooled vinyl radical journal December 2001
Fourier transform millimeter-wave spectroscopy of the deuterated vinyl radical, C2D3 journal June 2002
Two-layer Lanczos iteration approach to molecular spectroscopic calculation journal November 2002
Determination of the proton tunneling splitting of the vinyl radical in the ground state by millimeter-wave spectroscopy combined with supersonic jet expansion and ultraviolet photolysis journal February 2004
Electron Spin Resonance Studies of Transient Alkyl Radicals journal November 1963
Determination of Centrifugal Distortion Coefficients of Asymmetric‐Top Molecules journal March 1967
Infrared absorption and electron paramagnetic resonance studies of vinyl radical in noble-gas matrices journal August 2005
High-resolution infrared spectroscopy of jet-cooled vinyl radical: Symmetric CH2 stretch excitation and tunneling dynamics journal January 2008
Infrared absorption spectra of vinyl radicals isolated in solid Ne journal May 2008
Full-dimensional ab initio potential energy surface and vibrational configuration interaction calculations for vinyl journal May 2009
Full dimensional (15 dimensional) quantum-dynamical simulation of the protonated water-dimer IV: Isotope effects in the infrared spectra of D(D2O)2+, H(D2O)2+, and D(H2O)2+ isotopologues journal July 2009
Millimeter-wave spectroscopy of H2CCD: Tunneling splitting and ortho-para mixing interaction journal October 2010
The infrared spectra of C 2 H 4 + and C 2 H 3 trapped in solid neon journal February 2011
Large-amplitude dynamics in vinyl radical: The role of quantum tunneling as an isomerization mechanism journal January 2012
Iterative diagonalization in the state-averaged multi-configurational time-dependent Hartree approach: Excited state tunneling splittings in malonaldehyde journal February 2012
An ab initio determination of the rate constant for H2+C2H→H+C2H2 journal May 1982
Systematic GVB study of harmonic vibrational frequencies and dipole moment derivatives: The vinyl radical C 2 H 3 and other simple molecules journal June 1984
The vinyl radical investigated by infrared diode laser kinetic spectroscopy journal January 1990
Molecular potential energy surfaces by interpolation journal June 1994
Intensities and rates in the spectral domain without eigenvectors journal February 1996
Hyperfine coupling constants of organic radicals journal March 1997
Benchmark calculations with correlated molecular wave functions. VIII. Bond energies and equilibrium geometries of the CH n and C2Hn (n=1–4) series journal March 1997
Computing rovibrational levels of methane with curvilinear internal vibrational coordinates and an Eckart frame journal March 2013
Infrared spectroscopy and tunneling dynamics of the vinyl radical in 4 He nanodroplets journal May 2013
Vibrational spectroscopy of a transient species through time-resolved Fourier transform infrared emission spectroscopy: The vinyl radical journal June 2000
Permutation invariant polynomial neural network approach to fitting potential energy surfaces journal August 2013
Multi-layer Lanczos iteration approach to calculations of vibrational energies and dipole transition intensities for polyatomic molecules journal January 2015
Using multi-dimensional Smolyak interpolation to make a sum-of-products potential journal July 2015
Full-dimensional quantum dynamics study of the H 2 + C 2 H → H + C 2 H 2 reaction on an ab initio potential energy surface journal May 2016
Permutation invariant potential energy surfaces for polyatomic reactions using atomistic neural networks journal June 2016
The hydrogen tunneling splitting in malonaldehyde: A full-dimensional time-independent quantum mechanical method journal August 2016
An exact variational method to calculate rovibrational spectra of polyatomic molecules with large amplitude motion journal August 2016
Perspective: Accurate ro-vibrational calculations on small molecules journal September 2016
Perspective: Computing (ro-)vibrational spectra of molecules with more than four atoms journal March 2017
Communication: VSCF/VCI vibrational spectroscopy of H 7 O 3 + and H 9 O 4 + using high-level, many-body potential energy surface and dipole moment surfaces journal March 2017
Variational quantum approaches for computing vibrational energies of polyatomic molecules journal August 2008
Permutationally invariant potential energy surfaces in high dimensionality journal October 2009
Quantum approaches to polyatomic reaction dynamics journal March 2013
Representing potential energy surfaces by high-dimensional neural network potentials journal April 2014
Forces in Molecules journal August 1939
Perspective: Accurate ro-vibrational calculations on small molecules text January 2016

Cited By (4)

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
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

Similar Records

An exact variational method to calculate rovibrational spectra of polyatomic molecules with large amplitude motion
Journal Article · Sun Aug 28 00:00:00 EDT 2016 · Journal of Chemical Physics · OSTI ID:22678892
Photoionization study of the vinyl radical
Journal Article · Wed Jun 15 00:00:00 EDT 1988 · J. Chem. Phys.; (United States) · OSTI ID:5183071
Infrared spectroscopy and tunneling dynamics of the vinyl radical in 4He nanodroplets
Journal Article · Tue Apr 30 20:00:00 EDT 2013 · Journal of Chemical Physics · OSTI ID:1409045

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY