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Title: Vibrational control of the reaction pathway in the H + CHD 3 → H 2 + CD 3 reaction

Journal Article · · Science Advances
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [2]
  1. Universität Bielefeld (Germany); Stanford Univ., CA (United States); SLAC National Accelerator Lab., Menlo Park, CA (United States)
  2. Universität Bielefeld (Germany)
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An accurate full-dimensional quantum state-to-state simulation of the six-atom title reaction based on first-principles theory is reported. Counterintuitive effects are found: Increasing the energy in the reactant’s CD3 umbrella vibration reduces the energy in the corresponding product vibration. An in-depth analysis reveals the crucial role of the effective dynamical transition state: Its geometry is controlled by the vibrational states of the reactants and subsequently controls the quantum state distribution of the products. This finding enables generalizing the concept of transition state control of chemical reactions to the quantum state–specific level.

Research Organization:
SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
AC02-76SF00515
OSTI ID:
1866573
Journal Information:
Science Advances, Journal Name: Science Advances Journal Issue: 13 Vol. 8; ISSN 2375-2548
Publisher:
AAASCopyright Statement
Country of Publication:
United States
Language:
English

References (56)

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
The multi-configurational time-dependent Hartree approach journal January 1990
Modulations of Transition-State Control of State-to-State Dynamics in the F + H 2 O → HF + OH Reaction journal February 2015
State-to-State Mode Specificity: Energy Sequestration and Flow Gated by Transition State journal December 2015
Theoretical Study of the Validity of the Polanyi Rules for the Late-Barrier Cl + CHD 3 Reaction journal November 2012
Mode Selectivity for a “Central” Barrier Reaction: Eight-Dimensional Quantum Studies of the O( 3 P) + CH 4 → OH + CH 3 Reaction on an Ab Initio Potential Energy Surface journal December 2012
Loss of Memory in H + CH 4 → H 2 + CH 3 State-to-State Reactive Scattering journal January 2015
Revealing the stereospecific chemistry of the reaction of Cl with aligned CHD3(ν1 = 1) journal July 2012
Dynamical barrier and isotope effects in the simplest substitution reaction via Walden inversion mechanism journal February 2017
Recent advances in quantum scattering calculations on polyatomic bimolecular reactions journal January 2017
Natural reaction channels in H + CHD 3 → H 2 + CD 3 journal January 2018
A seven-dimensional quantum study of the H+CH4 reaction journal December 2002
Multilayer formulation of the multiconfiguration time-dependent Hartree theory journal July 2003
Quantum mechanical transition state theory and a new semiclassical model for reaction rate constants journal September 1974
Recent advances in crossed-beam studies of bimolecular reactions journal October 2006
Seven-dimensional quantum dynamics study of the O(P3)+CH4 reaction journal February 2007
Quantum dynamics of the CH3 fragment: A curvilinear coordinate system and kinetic energy operators journal October 2007
The state averaged multiconfigurational time-dependent Hartree approach: Vibrational state and reaction rate calculations journal February 2008
A multilayer multiconfigurational time-dependent Hartree approach for quantum dynamics on general potential energy surfaces journal April 2008
Layered discrete variable representations and their application within the multiconfigurational time-dependent Hartree approach journal February 2009
Quantum dynamics of the H+CH4→H2+CH3 reaction in curvilinear coordinates: Full-dimensional and reduced dimensional calculations of reaction rates journal February 2010
Communications: A rigorous transition state based approach to state-specific reaction dynamics: Full-dimensional calculations for H+CH4→H2+CH3 journal May 2010
A transition state view on reactive scattering: Initial state-selected reaction probabilities for the H+CH4→H2+CH3 reaction studied in full dimensionality journal November 2010
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
State-to-state reaction probabilities within the quantum transition state framework journal February 2012
Quantum mechanical rate constants for bimolecular reactions journal November 1983
Wave‐packet dynamics within the multiconfiguration Hartree framework: General aspects and application to NOCl journal September 1992
The cumulative reaction probability as eigenvalue problem journal September 1993
A time‐dependent discrete variable representation for (multiconfiguration) Hartree methods journal October 1996
A quantum model Hamiltonian to treat reactions of the type X+YCZ3→XY+CZ3: Application to O(3P)+CH4→OH+CH3 journal January 2000
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
Correlation functions for fully or partially state-resolved reactive scattering calculations journal June 2014
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
Rotational mode specificity in the Cl + CHD 3 → HCl + CD 3 reaction journal August 2014
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
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
Communication: State-to-state dynamics of the Cl + H 2 O → HCl + OH reaction: Energy flow into reaction coordinate and transition-state control of product energy disposal journal June 2015
An eight-dimensional quantum dynamics study of the Cl + CH4→ HCl + CH3 reaction journal October 2015
Mode specific dynamics of the H2 + CH3 → H + CH4 reaction studied using quasi-classical trajectory and eight-dimensional quantum dynamics methods journal October 2015
Communication: Mode specific quantum dynamics of the F + CHD 3 → HF + CD 3 reaction journal May 2016
Communication: Reactivity borrowing in the mode selective chemistry of H + CHD 3 → H 2 + CD 3 journal December 2017
Full-dimensional quantum dynamics calculations for H + CHD 3 → H 2 + CD 3 : The effect of multiple vibrational excitations journal June 2018
Global Potential Energy Surface for the H+CH 4 ↔H 2 +CH 3 Reaction using Neural Networks journal August 2014
Full-dimensional quantum mechanical calculations of the reaction probability of the H + CH 4 reaction based on a mixed Jacobi and Radau description journal May 2020
Tracking the energy flow along the reaction path journal July 2008
Depression of reactivity by the collision energy in the single barrier H + CD4 -> HD + CD3 reaction journal July 2010
Reactivity oscillation in the heavy–light–heavy Cl + CH 4 reaction journal April 2020
State-Specific Correlation of Coincident Product Pairs in the F + CD4 Reaction journal May 2003
First-Principles Theory for the H + CH4 -> H2 + CH3 Reaction journal December 2004
Do Vibrational Excitations of CHD3 Preferentially Promote Reactivity Toward the Chlorine Atom? journal June 2007
Breakdown of the Born-Oppenheimer Approximation in the F+ o-D2 -> DF + D Reaction journal August 2007
CH Stretching Excitation in the Early Barrier F + CHD3 Reaction Inhibits CH Bond Cleavage journal July 2009
Steric Control of the Reaction of CH Stretch-Excited CHD3 with Chlorine Atom journal February 2011
Experimental and Theoretical Differential Cross Sections for a Four-Atom Reaction: HD + OH -> H2O + D journal July 2011
Some Concepts in Reaction Dynamics journal May 1987
State-to-State Dynamics of Elementary Bimolecular Reactions journal May 2007

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