Removing the barrier to the calculation of activation energies

Mesele, Oluwaseun O.; Thompson, Ward H.

doi:10.1063/1.4964284

Title: Removing the barrier to the calculation of activation energies

Journal Article · Thu Oct 06 00:00:00 EDT 2016 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.4964284· OSTI ID:1329013

Mesele, Oluwaseun O. ^[1];

^[1]

Univ. of Kansas, Lawrence, KS (United States). Dept. of Chemistry

Approaches for directly calculating the activation energy for a chemical reaction from a simulation at a single temperature are explored with applications to both classical and quantum systems. The activation energy is obtained from a time correlation function that can be evaluated from the same molecular dynamics trajectories or quantum dynamics used to evaluate the rate constant itself and thus requires essentially no extra computational work.

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Research Organization:: Univ. of Kansas, Lawrence, KS (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: FG02-05ER15708

OSTI ID:: 1329013

Alternate ID(s):: OSTI ID: 1328056

Journal Information:: Journal of Chemical Physics, Vol. 145, Issue 13; ISSN 0021-9606

Publisher:: American Institute of Physics (AIP)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 19 works

Citation information provided by
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References (22)

Statistical mechanics of isomerization dynamics in liquids and the transition state approximation Chandler, David The Journal of Chemical Physics, Vol. 68, Issue 6 https://doi.org/10.1063/1.436049	journal	January 1978
An iteration method for the solution of the eigenvalue problem of linear differential and integral operators Lanczos, C. Journal of Research of the National Bureau of Standards, Vol. 45, Issue 4 https://doi.org/10.6028/jres.045.026	journal	October 1950
On the Molecular Mechanism of Water Reorientation Laage, Damien; Hynes, James T. The Journal of Physical Chemistry B, Vol. 112, Issue 45 https://doi.org/10.1021/jp805217u	journal	November 2008
Quantum mechanical rate constants for bimolecular reactions Miller, William H.; Schwartz, Steven D.; Tromp, John W. The Journal of Chemical Physics, Vol. 79, Issue 10 https://doi.org/10.1063/1.445581	journal	November 1983
Quantum flux operators and thermal rate constant: Collinear H+H ₂ Park, Tae Jun; Light, J. C. The Journal of Chemical Physics, Vol. 88, Issue 8 https://doi.org/10.1063/1.454702	journal	April 1988
A novel discrete variable representation for quantum mechanical reactive scattering via the S ‐matrix Kohn method Colbert, Daniel T.; Miller, William H. The Journal of Chemical Physics, Vol. 96, Issue 3 https://doi.org/10.1063/1.462100	journal	February 1992
Statistical Merchanics Applied to Chemical Kinetics. Tolman, Richard C. Journal of the American Chemical Society, Vol. 42, Issue 12 https://doi.org/10.1021/ja01457a008	journal	December 1920
Application of transition path sampling methods in catalysis: A new mechanism for CC bond formation in the methanol coupling reaction in chabazite Lo, Cynthia S.; Radhakrishnan, Ravi; Trout, Bernhardt L. Catalysis Today, Vol. 105, Issue 1 https://doi.org/10.1016/j.cattod.2005.04.005	journal	July 2005
Quantum Statistical Mechanical Theory of the Rate of Exchange Chemical Reactions in the Gas Phase Yamamoto, Tsunenobu The Journal of Chemical Physics, Vol. 33, Issue 1 https://doi.org/10.1063/1.1731099	journal	July 1960
Overcoming barriers in trajectory space: Mechanism and kinetics of rare events via Wang–Landau enhanced transition path sampling Borrero, Ernesto E.; Dellago, Christoph The Journal of Chemical Physics, Vol. 133, Issue 13 https://doi.org/10.1063/1.3496376	journal	October 2010
On the “direct” calculation of thermal rate constants. II. The flux-flux autocorrelation function with absorbing potentials, with application to the O+HCl→OH+Cl reaction Thompson, Ward H.; Miller, William H. The Journal of Chemical Physics, Vol. 106, Issue 1 https://doi.org/10.1063/1.474109	journal	January 1997
A Molecular Jump Mechanism of Water Reorientation Laage, D. Science, Vol. 311, Issue 5762 https://doi.org/10.1126/science.1122154	journal	February 2006
The stable states picture of chemical reactions. II. Rate constants for condensed and gas phase reaction models Grote, Richard F.; Hynes, James T. The Journal of Chemical Physics, Vol. 73, Issue 6 https://doi.org/10.1063/1.440485	journal	September 1980
The stable states picture of chemical reactions. I. Formulation for rate constants and initial condition effects Northrup, Scott H.; Hynes, James T. The Journal of Chemical Physics, Vol. 73, Issue 6 https://doi.org/10.1063/1.440484	journal	September 1980
On the Reorientation and Hydrogen-Bond Dynamics of Alcohols Vartia, Anthony A.; Mitchell-Koch, Katie R.; Stirnemann, Guillaume The Journal of Physical Chemistry B, Vol. 115, Issue 42 https://doi.org/10.1021/jp206875k	journal	October 2011
Activation energy for a model ferrous-ferric half reaction from transition path sampling Drechsel-Grau, Christof; Sprik, Michiel The Journal of Chemical Physics, Vol. 136, Issue 3 https://doi.org/10.1063/1.3677195	journal	January 2012
T RANSITION P ATH S AMPLING : Throwing Ropes Over Rough Mountain Passes, in the Dark Bolhuis, Peter G.; Chandler, David; Dellago, Christoph Annual Review of Physical Chemistry, Vol. 53, Issue 1 https://doi.org/10.1146/annurev.physchem.53.082301.113146	journal	October 2002
On transition‐state theory and the classical mechanics of collinear collisions Pechukas, Philip; McLafferty, Francis J. The Journal of Chemical Physics, Vol. 58, Issue 4 https://doi.org/10.1063/1.1679404	journal	February 1973
Fast Parallel Algorithms for Short-Range Molecular Dynamics Plimpton, Steve Journal of Computational Physics, Vol. 117, Issue 1 https://doi.org/10.1006/jcph.1995.1039	journal	March 1995
The missing term in effective pair potentials Berendsen, H. J. C.; Grigera, J. R.; Straatsma, T. P. The Journal of Physical Chemistry, Vol. 91, Issue 24 https://doi.org/10.1021/j100308a038	journal	November 1987
Quantum mechanical transition state theory and a new semiclassical model for reaction rate constants Miller, William H. The Journal of Chemical Physics, Vol. 61, Issue 5 https://doi.org/10.1063/1.1682181	journal	September 1974
Activation Energies from Transition Path Sampling Simulations Dellago, Christoph; Bolhuis, Peter G. Molecular Simulation, Vol. 30, Issue 11-12 https://doi.org/10.1080/08927020412331294869	journal	September 2004

Cited By (5)

Removing the barrier to the calculation of activation energies: Diffusion coefficients and reorientation times in liquid water Piskulich, Zeke A.; Mesele, Oluwaseun O.; Thompson, Ward H. The Journal of Chemical Physics, Vol. 147, Issue 13 https://doi.org/10.1063/1.4997723	journal	October 2017
Expanding the calculation of activation volumes: Self-diffusion in liquid water Piskulich, Zeke A.; Mesele, Oluwaseun O.; Thompson, Ward H. The Journal of Chemical Physics, Vol. 148, Issue 13 https://doi.org/10.1063/1.5023420	journal	April 2018
The activation energy for water reorientation differs between IR pump-probe and NMR measurements Piskulich, Zeke A.; Thompson, Ward H. The Journal of Chemical Physics, Vol. 149, Issue 16 https://doi.org/10.1063/1.5050203	journal	October 2018
Rate constants in spatially inhomogeneous systems Schile, Addison J.; Limmer, David T. The Journal of Chemical Physics, Vol. 150, Issue 19 https://doi.org/10.1063/1.5092837	journal	May 2019
On the temperature dependence of liquid structure Piskulich, Zeke A.; Thompson, Ward H. The Journal of Chemical Physics, Vol. 152, Issue 1 https://doi.org/10.1063/1.5135932	journal	January 2020

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