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Title: Mode specific dynamics of the H2 + CH3 → H + CH4 reaction studied using quasi-classical trajectory and eight-dimensional quantum dynamics methods

Journal Article · · Journal of Chemical Physics
DOI:https://doi.org/10.1063/1.4933240· OSTI ID:1469566
 [1];  [2];  [3]; ORCiD logo [4];  [3];  [2]
  1. Key Laboratory of Magnetic Resonance in Biological Systems, Wuhan (China). National Center for Magnetic Resonance in Wuhan, State Key Laboratory of Magnetic Resonance and Atomic and Molecular Physics, Wuhan Institute of Physics and Mathematics, Chinese Academy of Sciences; Hubei University for Nationalities (China). School of Chemical and Environmental Engineering
  2. Univ. of New Mexico, Albuquerque, NM (United States). Department of Chemistry and Chemical Biology
  3. Key Laboratory of Magnetic Resonance in Biological Systems, Wuhan (China). National Center for Magnetic Resonance in Wuhan, State Key Laboratory of Magnetic Resonance and Atomic and Molecular Physics, Wuhan Institute of Physics and Mathematics, Chinese Academy of Sciences
  4. Nanyang Technological University (Singapore). Division of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences
+ Show Author Affiliations

In this work, an eight-dimensional quantum dynamical model is proposed and applied to the title reaction. The reaction probabilities and integral cross sections have been determined for both the ground and excited vibrational states of the two reactants. The results indicate that the H2 stretching and CH3 umbrella modes, along with the translational energy, strongly promote the reactivity, while the CH3 symmetric stretching mode has a negligible effect. The observed mode specificity is confirmed by full-dimensional quasi-classical trajectory calculations. Lastly, the mode specificity can be interpreted by the recently proposed sudden vector projection model, which attributes the enhancement effects of the reactant modes to their strong couplings with the reaction coordinate at the transition state.

Research Organization:
Univ. of New Mexico, Albuquerque, NM (United States)
Sponsoring Organization:
USDOE
Grant/Contract Number:
FG02-05ER15694
OSTI ID:
1469566
Alternate ID(s):
OSTI ID: 1224229
Journal Information:
Journal of Chemical Physics, Vol. 143, Issue 15; ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)Copyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 12 works
Citation information provided by
Web of Science

References (82)

Accurate quantum calculations of the reaction rates for H∕D+CH4 journal February 2007
Accurate potential energy surface and quantum reaction rate calculations for the H+CH4→H2+CH3 reaction journal April 2006
Seven-dimensional quantum dynamics study of the O(P3)+CH4 reaction journal February 2007
Full-Dimensional Quantum Reaction Rate Calculations for H + CH 4 → H 2 + CH 3 on a Recent Potential Energy Surface † journal September 2010
Loss of Memory in H + CH 4 → H 2 + CH 3 State-to-State Reactive Scattering journal January 2015
Space‐fixed vs body‐fixed axes in atom‐diatomic molecule scattering. Sudden approximations journal January 1974
Quantum dynamics study of the isotopic effect on capture reactions: HD, D2+CH3 journal January 2003
Four-dimensional quantum scattering calculations on the H+CH4→H2+CH3 reaction journal August 1999
The role of the transition state in polyatomic reactions: Initial state-selected reaction probabilities of the H + CH 4 → H 2 + CH 3 reaction journal November 2014
Quantum dynamics of the H+CH4→H2+CH3 reaction in curvilinear coordinates: Full-dimensional and reduced dimensional calculations of reaction rates journal February 2010
Concepts in reaction dynamics journal May 1972
Effects of C–H stretch excitation on the H+CH4 reaction journal October 2005
The hydrogen abstraction reaction H+CH[sub 4]. I. New analytical potential energy surface based on fitting to ab initio calculations journal January 2009
Quantum Dynamics of the CH 4 + H → CH 3 + H 2 Reaction:  Full-Dimensional and Reduced Dimensionality Rate Constant Calculations † journal March 2001
Quantum dynamics study of isotope effect for H+CH4 reaction using the SVRT model journal May 2003
A reduced dimensionality, six-degree-of-freedom, quantum calculation of the H+CH4→H2+CH3 reaction journal August 2001
Generalized semirigid vibrating rotor target model for atom–poly reaction: Inclusion of umbrella mode for H+CH4 reaction journal August 2002
Comparison of Quantum Dynamics and Quantum Transition State Theory Estimates of the H + CH 4 Reaction Rate † journal April 2009
Mode Specificity, Bond Selectivity, and Product Energy Disposal in X + CH 4 /CHD 3 (X=H, F, O( 3 P), Cl, and OH) Hydrogen Abstraction Reactions: Perspective from Sudden Vector Projection Model journal May 2014
Ab initio rate constants from hyperspherical quantum scattering: Application to H+CH4→H2+CH3 journal February 2004
Computational Chemistry of Polyatomic Reaction Kinetics and Dynamics:  The Quest for an Accurate CH 5 Potential Energy Surface journal November 2007
Relative efficacy of vibrational vs. translational excitation in promoting atom-diatom reactivity: Rigorous examination of Polanyi's rules and proposition of sudden vector projection (SVP) model journal June 2013
ESR Study of the Kinetic Isotope Effect in the Reaction of H and D Atoms with CH 4 journal February 1970
Direct rate constant measurements for atomic hydrogen + methane .fwdarw. methyl + hydrogen, 897-1729 K, using the flash photolysis-shock tube technique journal January 1991
Kinetics of the C 2 H 3 + H 2 ⇄ H + C 2 H 4 and CH 3 + H 2 ⇄ H + CH 4 Reactions journal January 1996
Rate Constants for the CH 4 + H → CH 3 + H 2 Reaction Calculated with a Generalized Reduced-Dimensionality Method † journal September 2002
Effects of reagent vibrational excitation on the dynamics of the H + CHD 3 → H 2 + CD 3 reaction: A seven-dimensional time-dependent wave packet study journal July 2011
An improved treatment of spectator mode vibrations in reduced dimensional quantum dynamics: Application to the hydrogen abstraction reactions μ+CH4, H+CH4, D+CH4, and CH3+CH4 journal July 2009
Validation of variational transition state theory with multidimensional tunneling contributions against accurate quantum mechanical dynamics for H+CH4→H2+CH3 in an extended temperature interval journal July 2002
Quasi-Classical Trajectory Calculations Analyzing the Reactivity and Dynamics of Asymmetric Stretch Mode Excitations of Methane in the H + CH 4 Reaction journal September 2006
The Sudden Vector Projection Model for Reactivity: Mode Specificity and Bond Selectivity Made Simple journal October 2014
Depression of reactivity by the collision energy in the single barrier H + CD4 -> HD + CD3 reaction journal July 2010
Quasiclassical trajectory study of the reaction H+CH4(ν3=0,1)→CH3+H2 using a new ab initio potential energy surface journal October 2006
A comparison study of the H + CH4 and H + SiH4 reactions with eight-dimensional quantum dynamics: normal mode versus local mode in the reactant molecule vibration journal August 2014
An ab initio potential surface describing abstraction and exchange for H+CH4 journal January 2006
An exploratory study of reactant vibrational effects in CH 3 + H 2 and its isotopic variants journal April 1975
Rate coefficients and kinetic isotope effects of the X + CH 4 → CH 3 + HX (X = H, D, Mu) reactions from ring polymer molecular dynamics journal March 2013
Accurate calculations of reaction rates: predictive theory based on a rigorous quantum transition state concept journal June 2011
A theoretical study of deuterium isotope effects in the reactions molecular hydrogen + methyl and atomic hydrogen + methane journal January 1984
A Reinterpretation of the Mechanism of the Simplest Reaction at an sp 3 -Hybridized Carbon Atom:  H + CD 4 → CD 3 + HD journal August 2005
Full‐dimensional time‐dependent treatment for diatom–diatom reactions: The H 2 +OH reaction journal July 1994
A permutationally invariant full-dimensional ab initio potential energy surface for the abstraction and exchange channels of the H + CH 4 system journal May 2015
Quantum mechanical close coupling approach to molecular collisions. j z ‐conserving coupled states approximation journal March 1974
First-Principles Theory for the H + CH4 -> H2 + CH3 Reaction journal December 2004
Vectorization of the general Monte Carlo classical trajectory program VENUS journal October 1991
A comparative study of potential energy surfaces for CH 3 +H 2 ↔CH 4 +H journal December 1987
Solution of the Schrödinger equation by a spectral method journal September 1982
A new potential energy surface for the CH 3 +H 2 ↔CH 4 +H reaction: Calibration and calculations of rate constants and kinetic isotope effects by variational transition state theory and semiclassical tunneling calculations journal December 1987
State‐to‐state dynamics of atom + polyatom abstraction reactions. I. The H+CD 4 →HD( v ’, J  ’)+CD 3 reaction journal February 1992
Path integral calculation of thermal rate constants within the quantum instanton approximation: Application to the H+CH4→H2+CH3 hydrogen abstraction reaction in full Cartesian space journal February 2004
A seven-dimensional quantum study of the H+CH4 reaction journal December 2002
H + CD 4 Abstraction Reaction Dynamics:  Excitation Function and Angular Distributions † journal January 2006
A transition state wave packet study of the H+CH4 reaction journal December 2007
The thermal reaction rate of muonium with methane (and ethane) in the gas phase journal March 1995
A time-dependent quantum dynamics study of the H2+CH3→H+CH4 reaction journal December 2002
Thermochemistry and Accurate Quantum Reaction Rate Calculations for H 2 /HD/D 2 + CH 3 † journal October 2007
Control of Mode/Bond Selectivity and Product Energy Disposal by the Transition State: X + H 2 O (X = H, F, O( 3 P), and Cl) Reactions journal September 2013
Reaction dynamics with the multi-layer multi-configurational time-dependent Hartree approach: H + CH 4 → H 2 + CH 3 rate constants for different potentials journal December 2012
Communication: Ro-vibrational control of chemical reactivity in H+CH 4 → H 2 +CH 3 : Full-dimensional quantum dynamics calculations and a sudden model journal August 2014
New analytical potential energy surface for the CH4+H hydrogen abstraction reaction: Thermal rate constants and kinetic isotope effects journal June 2002
Recalibration of Two Earlier Potential Energy Surfaces for the CH 4 + H → CH 3 + H 2 Reaction. Application of Variational Transition-State Theory and Analysis of the Kinetic Isotope Effects Using Rectilinear and Curvilinear Coordinates journal January 1996
Energy efficiency in surmounting the central energy barrier: a quantum dynamics study of the OH + CH 3 → O + CH 4 reaction journal January 2015
Application of semirigid vibrating rotor target model to reaction of H+CH4→CH3+H2 journal August 2000
H + CD 4 Abstraction Reaction Dynamics:  Product Energy Partitioning † journal March 2006
The hydrogen abstraction reaction H+CH[sub 4]. II. Theoretical investigation of the kinetics and dynamics journal January 2009
Full-dimensional and reduced-dimensional calculations of initial state-selected reaction probabilities studying the H + CH 4 → H 2 + CH 3 reaction on a neural network PES journal February 2015
Kinetics of Reactions of H Atoms With Methane and Chlorinated Methanes journal April 2001
Full dimensional quantum calculations of the CH[sub 4]+H→CH[sub 3]+H[sub 2] reaction rate journal January 2000
A novel discrete variable representation for quantum mechanical reactive scattering via the S ‐matrix Kohn method journal February 1992
Variational Transition State Theory journal October 1984
Theoretical study of the dynamics of the H+CH4 and H+C2H6 reactions using a specific-reaction-parameter semiempirical Hamiltonian journal May 2008
Ab initio potential energy surface and quantum dynamics for the H + CH 4 → H 2 + CH 3 reaction journal February 2011
Vibrational excitation in the transition state: The CH4+H→CH3+H2 reaction rate constant in an extended temperature interval journal February 2002
Communication: A six-dimensional state-to-state quantum dynamics study of the H + CH 4 → H 2 + CH 3 reaction ( J = 0) journal January 2013
ESR Study of the Kinetics of the Reaction of H Atoms with Methane journal June 1969
An eight-dimensional quantum mechanical Hamiltonian for X + YCZ 3 system and its applications to H + CH 4 reaction journal November 2012
Rate constants for H + CH4, CH3 + H2, and CH4 dissociation at high temperature journal January 2001
Tests of potential energy surfaces for H+CH4↔CH3+H2: Deuterium and muonium kinetic isotope effects for the forward and reverse reaction journal December 2002
Theoretical rate constants and kinetic isotope effects in the reaction of methane with H, D, T, and Mu atoms journal January 2008
Effects of reagent rotational excitation on the H + CHD 3 → H 2 + CD 3 reaction: A seven dimensional time-dependent wave packet study journal October 2014
Evaluated Kinetic Data for Combustion Modeling: Supplement II journal September 2005
A quantum model Hamiltonian to treat reactions of the type X+YCZ3→XY+CZ3: Application to O(3P)+CH4→OH+CH3 journal January 2000

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Full dimensional quantum mechanical calculations of the reaction probability of the H + NH 3 collision based on a mixed Jacobi and Radau description journal May 2019
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