skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Theoretical H + O3 rate coefficients from ring polymer molecular dynamics on an accurate global potential energy surface: assessing experimental uncertainties

Journal Article · · Physical Chemistry Chemical Physics. PCCP
DOI:https://doi.org/10.1039/d0cp05771a· OSTI ID:1852058
 [1]; ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [1]
  1. Nanjing Univ. (China)
  2. Univ. of New Mexico, Albuquerque, NM (United States)
+ Show Author Affiliations

Thermal rate coefficients and kinetic isotope effects have been calculated for an important atmospheric reaction H/D + O3 → OH/OD + O2 based on an accurate permutation invariant polynomial-neural network potential energy surface, using ring polymer molecular dynamics (RPMD), quasi-classical trajectory (QCT) and variational transition-state theory (VTST) with multidimensional tunneling. The RPMD approach yielded results that are generally in better agreement with experimental rate coefficients than the VTST and QCT ones, especially at low temperatures, attributable to its capacity to capture quantum effects such as tunneling and zero-point energy. Additionally, the theoretical results support one group of existing experiments over the other. In addition, rate coefficients for the D + O3 → OD + O2 reaction are also reported using the same methods, which will allow a stringent assessment of future experimental measurements, thus helping to reduce the uncertainty in the recommended rate coefficients of this reaction.

Research Organization:
Univ. of New Mexico, Albuquerque, NM (United States)
Sponsoring Organization:
USDOE Office of Science (SC); National Natural Science Foundation of China (NSFC); Fundamental Research Funds for the Central Universities
Grant/Contract Number:
SC0015997; U1932147; 22073042; 21733006; 14380016
OSTI ID:
1852058
Alternate ID(s):
OSTI ID: 1765440
Journal Information:
Physical Chemistry Chemical Physics. PCCP, Vol. 23, Issue 5; ISSN 1463-9076
Publisher:
Royal Society of ChemistryCopyright Statement
Country of Publication:
United States
Language:
English

References (97)

A ring polymer molecular dynamics study of the Cl + O3 reaction journal January 2014
Improved Dual-Level Direct Dynamics Method for Reaction Rate Calculations with Inclusion of Multidimensional Tunneling Effects and Validation for the Reaction of H with trans -N 2 H 2 journal May 1997
Ring-Polymer Molecular Dynamics for the Prediction of Low-Temperature Rates: An Investigation of the C( 1 D) + H 2 Reaction journal October 2015
A VTST Study of the H + O 3 and O + HO 2 Reactions Using a Six-dimensional DMBE Potential Energy Surface for Ground State HO 3 journal April 2002
The Thermodynamics of the Elusive HO3 Radical journal June 2010
Riddles of the structure and vibrational dynamics of HO 3 resolved near the ab initio limit journal September 2019
Critical Survey of Data on the Spectroscopy and Kinetics of Ozone in the Mesosphere and Thermosphere
  • Steinfeld, Jeffrey I.; Adler‐Golden, Steven M.; Gallagher, Jean W.
  • Journal of Physical and Chemical Reference Data, Vol. 16, Issue 4 https://doi.org/10.1063/1.555796
journal October 1987
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
Dynamics Study of the O + HO 2 Reaction Using Two DMBE Potential Energy Surfaces:  The Role of Vibrational Excitation † journal October 2004
Low temperature kinetics: the association of OH radicals with O2 journal January 2010
Dynamics of H + HeH + ( v = 0, j = 0) → H 2 + + He: Insight on the Possible Complex-Forming Behavior of the Reaction journal November 2019
Yields of HO 2 in the reaction of hydrogen atoms with ozone journal March 1980
Direct dynamics calculation of the kinetic isotope effect for an organic hydrogen-transfer reaction, including corner-cutting tunneling in 21 dimensions journal August 1993
Advances and New Challenges to Bimolecular Reaction Dynamics Theory journal September 2020
Ring-Polymer Molecular Dynamics: Quantum Effects in Chemical Dynamics from Classical Trajectories in an Extended Phase Space journal April 2013
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
Quasiclassical Trajectory Study of the Environmental Reaction O + HO 2 → OH + O 2 journal August 1998
A practical implementation of semi-classical transition state theory for polyatomics journal October 2010
VTST and RPMD kinetics study of the nine-body X + C 2 H 6 (X ≡ H, Cl, F) reactions based on analytical potential energy surfaces journal January 2020
Statistical mechanics of isomerization dynamics in liquids and the transition state approximation journal January 1978
Mass Spectrometric Studies of Atomic Reactions. III. Reactions of Hydrogen Atoms with Nitrogen Dioxide and with Ozone journal September 1962
Vectorization of the general Monte Carlo classical trajectory program VENUS journal October 1991
Is HO3 minimum cis or trans? An analytic full-dimensional ab initio isomerization path journal January 2011
Atomic hydrogen in the mesopause region derived from SABER: Algorithm theoretical basis, measurement uncertainty, and results journal March 2014
Dynamics of H(D)+O3 reactions on a double many-body expansion potential-energy surface for ground state HO3 journal January 1997
Ring-polymer molecular dynamics rate-theory in the deep-tunneling regime: Connection with semiclassical instanton theory journal December 2009
Double many-body expansion potential energy surface for ground-state HO3 journal June 1997
Quantum statistics and classical mechanics: Real time correlation functions from ring polymer molecular dynamics journal August 2004
Dissociation Energy of the HOOO Radical journal October 2009
Rate Coefficients of the HCl + OH → Cl + H 2 O Reaction from Ring Polymer Molecular Dynamics journal May 2016
Kinetics and dynamics study of the OH + C 2 H 6 → H 2 O + C 2 H 5 reaction based on an analytical global potential energy surface journal January 2020
RPMDrate: Bimolecular chemical reaction rates from ring polymer molecular dynamics journal March 2013
The Rotational Spectrum and Structure of the HOOO Radical journal June 2005
Ab initio study of the elusive HO3(X2A″) radical and the reaction journal December 2013
The definition of reaction coordinates for reaction‐path dynamics journal June 1991
Ring-Polymer Molecular Dynamics Rate Coefficient Calculations for Insertion Reactions: X + H 2 → HX + H (X = N, O) journal January 2014
Reaction‐path potential and vibrational frequencies in terms of curvilinear internal coordinates journal February 1995
Evaluated Kinetic and Photochemical Data for Atmospheric Chemistry: Supplement I CODATA Task Group on Chemical Kinetics journal April 1982
Accurate Determination of Tunneling-Affected Rate Coefficients: Theory Assessing Experiment journal July 2017
Chemical reaction rates from ring polymer molecular dynamics journal February 2005
Ab initio theoretical calculation and potential energy surface for ground-state HO3 journal February 2001
Force-field calculation and geometry of the HOOO radical journal September 2013
Formation of Vibrationally Excited OH by the Reaction H + O_3 journal January 1971
Ring-polymer molecular dynamics studies on the rate coefficient of the abstraction channel of hydrogen plus ethane, propane, and dimethyl ether journal January 2017
New Stress Test for Ring Polymer Molecular Dynamics: Rate Coefficients of the O( 3 P) + HCl Reaction and Comparison with Quantum Mechanical and Quasiclassical Trajectory Results journal August 2019
Initial distribution of vibration of the OH radicals produced in the H + O3 → OH(X2Π1/2,3/2) + O2 reaction. Chemiluminescence by a crossed beam technique journal July 1985
Weakly Bound Molecules in the Atmosphere: A Case Study of HOOO journal March 2009
Infrared chemiluminescence studies using a SISAM spectrometer. Reactions producing vibrationally excited OH journal January 1987
Relative Energies and Geometries of the cis - and trans -HO 3 Radicals from the Parametric 2-Electron Density Matrix Method journal February 2013
What are the Implications of Nonequilibrium in the O+OH and O+HO2 Reactions? journal March 2005
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
On the Dissociation of Ground State trans -HOOO Radical: A Theoretical Study journal August 2010
Recrossing and Tunneling in the Kinetics Study of the OH + CH 4 → H 2 O + CH 3 Reaction journal April 2015
Analysis of the HOOO torsional potential journal January 2011
Exploiting the isomorphism between quantum theory and classical statistical mechanics of polyatomic fluids journal April 1981
Rigorous formulation of quantum transition state theory and its dynamical corrections journal December 1989
Atomic resonance fluorescence for rate constants of rapid bimolecular reactions. Part 5—Hydrogen atom reactions; H + NO 2 and H + O 3 journal January 1977
Chemical Reaction Rate Coefficients from Ring Polymer Molecular Dynamics: Theory and Practical Applications journal September 2016
Quantum Dynamical Rate Constant for the H + O 3 Reaction Using a Six-Dimensional Double Many-Body Expansion Potential Energy Surface journal November 1997
Ring-polymer molecular dynamics studies of thermal rate coefficients for reaction F + H 2 O → HF + OH journal June 2019
Absolute rate constant and temperature dependence of the reaction between hydrogen (2S) atoms and ozone journal March 1979
Ring-polymer molecular dynamical benchmarks for X + H2 insertion reactions journal September 2019
On the stability of the elusive HO3 radical journal January 2011
Absolute concentrations of highly vibrationally excited OH(υ = 9 + 8) in the mesopause region derived from the TIMED/SABER instrument journal February 2013
A three-dimensional quantum mechanical study of the O+HO2 atmospheric reaction: infinite-order sudden approximation and novel adiabatic approaches vs. quasiclassical trajectories journal October 1998
Rattle: A “velocity” version of the shake algorithm for molecular dynamics calculations journal October 1983
Rate coefficients of the H + H 2 O 2 → H 2 + HO 2 reaction on an accurate fundamental invariant-neural network potential energy surface journal November 2018
Theoretical Investigations of Rate Coefficients of H + H 2 O 2 → OH + H 2 O on a Full-Dimensional Potential Energy Surface journal April 2019
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
OH Emission Bands in the Spectrum of the Night Sky. journal March 1950
Molecular dynamics simulations at constant pressure and/or temperature journal February 1980
A refined ring polymer molecular dynamics theory of chemical reaction rates journal July 2005
Quantum Roaming in the Complex-Forming Mechanism of the Reactions of OH with Formaldehyde and Methanol at Low Temperature and Zero Pressure: A Ring Polymer Molecular Dynamics Approach journal March 2019
Chemical Reaction Rates from Ring Polymer Molecular Dynamics: Zero Point Energy Conservation in Mu + H 2 → MuH + H journal January 2012
Ring Polymer Molecular Dynamics in Gas–Surface Reactions: Inclusion of Quantum Effects Made Simple journal November 2019
An experimental and theoretical investigation of the C( 1 D) + D 2 reaction journal January 2017
Time-resolved emission studies of vibrationally excited hydroxyl radicals: OH(X 2 π, v″=9) journal January 1982
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
The production of O( 3 P ) and ground state OH in the reaction of hydrogen atoms with ozone journal April 1981
Bimolecular reaction rates from ring polymer molecular dynamics: Application to H + CH 4 → H 2 + CH 3 journal January 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
Quantum Dynamical Rate Constant for the H + O 3 Reaction Using a Six-Dimensional Double Many-Body Expansion Potential Energy Surface Revisited journal November 1998
Absolute rate of the reaction of hydrogen atoms with ozone from 219–360 K journal January 1978
Ab Initio Treatment of Bond-Breaking Reactions: Accurate Course of HO 3 Dissociation and Revisit to Isomerization journal January 2012
Thermal Rate Coefficients for the Astrochemical Process C + CH + → C 2 + + H by Ring Polymer Molecular Dynamics journal December 2016
A Theoretical Study of the Potential Energy Surface and Rate Constant for an O( 3 P) + HO 2 Reaction journal April 2000
Theoretical Investigations of Rate Coefficients for H + O 3 and HO 2 + O Reactions on a Full-Dimensional Potential Energy Surface journal July 2020
Laser Measurements of the H Atom + Ozone Rate Constant at Mesospheric Temperatures journal May 2016
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
A Ring Polymer Molecular Dynamics Approach to Study the Transition between Statistical and Direct Mechanisms in the H 2 + H 3 + → H 3 + + H 2 Reaction journal April 2018
Observation of ν1+νn combination bands of the HOOO and DOOO radicals using infrared action spectroscopy journal June 2008
Quantum simulation of hydrogen in metals journal February 1987
Ring-polymer molecular dynamics study on rate coefficient of the barrierless OH + CO system at low temperature journal January 2019
Generalized transition state theory. Bond energy-bond order method for canonical variational calculations with application to hydrogen atom transfer reactions journal August 1979

Similar Records

Dissection of the multichannel reaction of acetylene with atomic oxygen: from the global potential energy surface to rate coefficients and branching dynamics
Journal Article · Mon Dec 10 00:00:00 EST 2018 · Physical Chemistry Chemical Physics. PCCP · OSTI ID:1852058
+2 more
Communication: Rate coefficients of the H + CH{sub 4} → H{sub 2} + CH{sub 3} reaction from ring polymer molecular dynamics on a highly accurate potential energy surface
Journal Article · Mon Sep 14 00:00:00 EDT 2015 · Journal of Chemical Physics · OSTI ID:1852058
Kinetic isotope effects: Theoretical prediction of the thermal rate coefficient for the reaction D+O/sub 2/. -->. OD+O
Journal Article · Tue Dec 01 00:00:00 EST 1981 · J. Chem. Phys.; (United States) · OSTI ID:1852058

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
71 CLASSICAL AND QUANTUM MECHANICS
GENERAL PHYSICS