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Title: Chemical Reaction Rate Coefficients from Ring Polymer Molecular Dynamics: Theory and Practical Applications

Journal Article · · Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory
 [1];  [2];  [3]
  1. Cyprus Inst., Nicosia (Cyprus); Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)
  2. Complutense Univ. of Madrid (Spain)
  3. Univ. of New Mexico, Albuquerque, NM (United States)
+ Show Author Affiliations

This Feature Article presents an overview of the current status of ring polymer molecular dynamics (RPMD) rate theory. We first analyze the RPMD approach and its connection to quantum transition-state theory. We then focus on its practical applications to prototypical chemical reactions in the gas phase, which demonstrate how accurate and reliable RPMD is for calculating thermal chemical reaction rate coefficients in multifarious cases. This review serves as an important checkpoint in RPMD rate theory development, which shows that RPMD is shifting from being just one of recent novel ideas to a well-established and validated alternative to conventional techniques for calculating thermal chemical rate coefficients. We also hope it will motivate further applications of RPMD to various chemical reactions.

Research Organization:
Univ. of New Mexico, Albuquerque, NM (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
FG02-05ER15694; SC0015997
OSTI ID:
1326705
Alternate ID(s):
OSTI ID: 1333914
Journal Information:
Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory, Journal Name: Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory Vol. 120 Journal Issue: 43; ISSN 1089-5639
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 110 works
Citation information provided by
Web of Science

References (102)

Communication: Relation of centroid molecular dynamics and ring-polymer molecular dynamics to exact quantum dynamics journal May 2015
Loss of Memory in H + CH 4 → H 2 + CH 3 State-to-State Reactive Scattering journal January 2015
Theoretical Studies of Polyatomic Bimolecular Reaction Dynamics journal October 1995
A ring polymer molecular dynamics study of the Cl + O3 reaction journal January 2014
Quantum mechanical rate constants for bimolecular reactions journal November 1983
Ring-Polymer Molecular Dynamics for the Prediction of Low-Temperature Rates: An Investigation of the C( 1 D) + H 2 Reaction journal October 2015
Erratum: “Bimolecular reaction rates from ring polymer molecular dynamics” [J. Chem. Phys. 130, 174713 (2009)] journal July 2010
Neural Networks in Chemical Reaction Dynamics January 2012
Communication: Rate coefficients of the H + CH 4 → H 2 + CH 3 reaction from ring polymer molecular dynamics on a highly accurate potential energy surface journal September 2015
Comparison of Quantum Dynamics and Quantum Transition State Theory Estimates of the H + CH 4 Reaction Rate † journal April 2009
Ring-polymer molecular dynamical calculations for the F + HCl → HF + Cl reaction on the ground 1 2 A′ potential energy surface journal January 2016
Bimolecular reaction rates from ring polymer molecular dynamics journal May 2009
Rate Coefficient for the 4 Heμ + CH 4 Reaction at 500 K: Comparison between Theory and Experiment journal November 2015
Perspective: Nonadiabatic dynamics theory journal December 2012
Analysis of the statistical error in umbrella sampling simulations by umbrella integration journal June 2006
Potential energy surface for a seven-atom reaction. Thermal rate constants and kinetic isotope effects for CH4+OH journal April 2000
Theory of Coupled Electron and Proton Transfer Reactions journal December 2010
Ring-Polymer Molecular Dynamics: Quantum Effects in Chemical Dynamics from Classical Trajectories in an Extended Phase Space journal April 2013
Surface Diffusion of Hydrogen on Ni(100) from Ring Polymer Molecular Dynamics journal May 2012
Bridging the gap between thermodynamic integration and umbrella sampling provides a novel analysis method: “Umbrella integration” journal October 2005
An efficient ring polymer contraction scheme for imaginary time path integral simulations journal July 2008
Quantum Rate Coefficients and Kinetic Isotope Effect for the Reaction Cl + CH 4 → HCl + CH 3 from Ring Polymer Molecular Dynamics journal March 2014
Chemical Kinetics and Mechanisms of Complex Systems: A Perspective on Recent Theoretical Advances journal January 2014
Experimental and Theoretical Differential Cross Sections for a Four-Atom Reaction: HD + OH -> H2O + D journal July 2011
The reactions CHnD4−n+OH→P and CH4+OD→CH3+HOD as a test of current direct dynamics multicoefficient methods to determine variational transition state rate constants. II journal September 2001
Statistical mechanics of isomerization dynamics in liquids and the transition state approximation journal January 1978
On the efficient path integral evaluation of thermal rate constants within the quantum instanton approximation journal February 2004
Ring-polymer molecular dynamics rate-theory in the deep-tunneling regime: Connection with semiclassical instanton theory journal December 2009
A kinetic study of hydroxyl radical reactions with methane and perdeuterated methane journal October 1993
Quantum statistics and classical mechanics: Real time correlation functions from ring polymer molecular dynamics journal August 2004
Rate Coefficients of the HCl + OH → Cl + H 2 O Reaction from Ring Polymer Molecular Dynamics journal May 2016
Quantum dynamics of complex-forming bimolecular reactions journal January 2012
A new formulation of quantum transition state theory for adiabatic rate constants journal October 1994
RPMDrate: Bimolecular chemical reaction rates from ring polymer molecular dynamics journal March 2013
A New Approach to Quantum-Statistical Mechanics journal October 1955
Test of variational transition state theory with multidimensional tunneling contributions against experimental kinetic isotope effects for the CH n D 4−n + OH→P (n=0, 4) reactions
  • Masgrau, Laura; González-Lafont, Àngels; Lluch, José M.
  • Theoretical Chemistry Accounts: Theory, Computation, and Modeling (Theoretica Chimica Acta), Vol. 108, Issue 1 https://doi.org/10.1007/s00214-002-0357-7
journal July 2002
How to remove the spurious resonances from ring polymer molecular dynamics journal June 2014
On the short-time limit of ring polymer molecular dynamics journal September 2006
Quantum-classical crossover of the transition rate in the damped double well journal August 1987
A ring polymer molecular dynamics study of the isotopologues of the H + H2 reaction journal January 2013
Ring-Polymer Molecular Dynamics Rate Coefficient Calculations for Insertion Reactions: X + H 2 → HX + H (X = N, O) journal January 2014
Boltzmann-conserving classical dynamics in quantum time-correlation functions: “Matsubara dynamics” journal April 2015
Fate of the false vacuum. II. First quantum corrections journal September 1977
Which Is Better at Predicting Quantum-Tunneling Rates: Quantum Transition-State Theory or Free-Energy Instanton Theory? journal November 2014
Communication: Full dimensional quantum rate coefficients and kinetic isotope effects from ring polymer molecular dynamics for a seven-atom reaction OH + CH 4 → CH 3 + H 2 O journal June 2013
Kinetically constrained ring-polymer molecular dynamics for non-adiabatic chemical reactions journal February 2014
Interpolated variational transition state theory and tunneling calculations of the rate constant of the reaction OH+CH 4 at 223–2400 K journal July 1993
Chemical reaction rates from ring polymer molecular dynamics journal February 2005
Tunneling Above the Crossover Temperature journal December 2013
Correlated double-proton transfer. I. Theory journal November 2007
Dynamics and dissipation in enzyme catalysis journal September 2011
Properties of Quantum Transition State Theory and Its Corrections journal January 1996
Tunneling splitting and decay of metastable states in polyatomic molecules: invariant instanton theory journal January 2008
Rate Coefficients for the Reactions of Hydroxyl Radicals with Methane and Deuterated Methanes journal April 1997
Theoretical Kinetics Study of the F( 2 P) + NH 3 Hydrogen Abstraction Reaction journal January 2014
Derivation of a true ( t → 0 + ) quantum transition-state theory. I. Uniqueness and equivalence to ring-polymer molecular dynamics transition-state-theory journal February 2013
Derivation of a true ( t → 0 + ) quantum transition-state theory. II. Recovery of the exact quantum rate in the absence of recrossing journal August 2013
Carbon kinetic isotope effect in the oxidation of methane by the hydroxyl radical journal January 1990
On the uniqueness of t → 0 + quantum transition-state theory journal August 2013
Recrossing and Tunneling in the Kinetics Study of the OH + CH 4 → H 2 O + CH 3 Reaction journal April 2015
Ring polymer molecular dynamics with surface hopping journal December 2012
High-dimensional ab initio potential energy surfaces for reaction dynamics calculations journal January 2011
Direct simulation of proton-coupled electron transfer across multiple regimes journal April 2013
Rigorous formulation of quantum transition state theory and its dynamical corrections journal December 1989
Should thermostatted ring polymer molecular dynamics be used to calculate thermal reaction rates? journal August 2015
Communication: Nonadiabatic ring-polymer molecular dynamics journal July 2013
The reactions CHnD4−n+OH→P and CH4+OD→CH3+HOD as a test of current direct dynamics computational methods to determine variational transition-state rate constants. I. journal February 2001
Generalized path integral based quantum transition state theory journal October 1997
Ring polymer molecular dynamics fast computation of rate coefficients on accurate potential energy surfaces in local configuration space: Application to the abstraction of hydrogen from methane journal April 2016
Theoretical Kinetics Study of the O( 3 P) + CH 4 /CD 4 Hydrogen Abstraction Reaction: The Role of Anharmonicity, Recrossing Effects, and Quantum Mechanical Tunneling journal April 2014
Semiclassical limit of quantum mechanical transition state theory for nonseparable systems journal March 1975
Deuterium and carbon‐13 kinetic isotope effects for the reaction of OH with CH 4 journal September 1993
Q UANTUM S CATTERING C ALCULATIONS ON C HEMICAL R EACTIONS journal October 2003
Prediction of Experimentally Unavailable Product Branching Ratios for Biofuel Combustion: The Role of Anharmonicity in the Reaction of Isobutanol with OH journal March 2014
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
A refined ring polymer molecular dynamics theory of chemical reaction rates journal July 2005
Chemical Reaction Rates from Ring Polymer Molecular Dynamics: Zero Point Energy Conservation in Mu + H 2 → MuH + H journal January 2012
First-Principles Theory for the H + CH4 -> H2 + CH3 Reaction journal December 2004
Nonadiabatic Quantum Chemistry—Past, Present, and Future journal November 2011
Ring-polymer molecular dynamics: Rate coefficient calculations for energetically symmetric (near thermoneutral) insertion reactions (X + H2) → HX + H(X = C(1D), S(1D)) journal December 2014
Bimolecular reaction rates from ring polymer molecular dynamics: Application to H + CH 4 → H 2 + CH 3 journal January 2011
Modeling the Kinetics of Bimolecular Reactions journal November 2006
Direct simulation of electron transfer using ring polymer molecular dynamics: Comparison with semiclassical instanton theory and exact quantum methods journal August 2011
Stress Test for Quantum Dynamics Approximations: Deep Tunneling in the Muonium Exchange Reaction D + HMu → DMu + H
  • Pérez de Tudela, Ricardo; Suleimanov, Yury V.; Richardson, Jeremy O.
  • The Journal of Physical Chemistry Letters, Vol. 5, Issue 23 https://doi.org/10.1021/jz502216g
journal November 2014
On the equivalence of two commonly used forms of semiclassical instanton theory journal March 2011
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
Future perspectives of nonadiabatic chemical dynamics journal January 2010
Semiclassical transition state theory for nonseparable systems: Application to the collinear H+H 2 reaction journal September 1975
Accurate molecular dynamics and nuclear quantum effects at low cost by multiple steps in real and imaginary time: Using density functional theory to accelerate wavefunction methods journal February 2016
Ab initio molecular dynamics with nuclear quantum effects at classical cost: Ring polymer contraction for density functional theory journal February 2016
Quantum Dynamics Study of the F + CH 4 → HF + CH 3 Reaction on an Ab Initio Potential Energy Surface journal May 2013
Quantum instanton approximation for thermal rate constants of chemical reactions journal July 2003
Ring Polymer Molecular Dynamics Calculations of Thermal Rate Constants for the O( 3 P) + CH 4 → OH + CH 3 Reaction: Contributions of Quantum Effects journal December 2012
Quantum simulation of hydrogen in metals journal February 1987
Quantum ring-polymer contraction method: Including nuclear quantum effects at no additional computational cost in comparison to ab initio molecular dynamics journal April 2016
Quantum instanton calculation of rate constant for CH 4 + OH → CH 3 + H 2 O reaction: Torsional anharmonicity and kinetic isotope effect journal December 2012
Simulating Excited State Dynamics in Systems with Multiple Avoided Crossings Using Mapping Variable Ring Polymer Molecular Dynamics journal October 2015
From ab Initio Potential Energy Surfaces to State-Resolved Reactivities: X + H 2 O ↔ HX + OH [X = F, Cl, and O( 3 P)] Reactions journal May 2015
Accurate quantum dynamics of a combustion reaction: Thermal rate constants of O(3P)+CH4(X 1A1)→OH(X 2Π)+CH3(X 2A2″) journal September 2002
Recent Advances in Quantum Dynamics of Bimolecular Reactions journal May 2016
An alternative derivation of ring-polymer molecular dynamics transition-state theory journal May 2016
A refined ring polymer contraction scheme for systems with electrostatic interactions journal October 2008

Figures / Tables (7)

Table 1(p. 6)table Table 1
Table 2(p. 7)table Table 2
Figure 1(p. 8)figure Figure 1
Figure 2(p. 8)figure Figure 2
Figure 3(p. 9)figure Figure 3
Table 3(p. 9)table Table 3
Figure 4(p. 10)figure Figure 4

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