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Title: Kinetics and dynamics of the C( 3P) + H 2 O reaction on a full-dimensional accurate triplet state potential energy surface

Abstract

A full dimensional accurate potential energy surface (PES) for the C( 3P) and H 2O reaction is developed based on ~34 000 data points calculated at the level of the explicitly correlated unrestricted coupled cluster method with single, double, and perturbative triple excitations with the augmented correlation-consistent polarized triple zeta basis set (CCSD(T)-F12a/AVTZ). The PES is invariant with respect to the permutation of the two hydrogen atoms and the total root mean square error (RMSE) of the fit is only 0.31 kcal mol -1. The PES features two barriers in the entrance channel and several potential minima, as well as multiple product channels. The rate coefficients of this reaction calculated using a transition-state theory and quasi-classical trajectory (QCT) method are small near room temperature, consistent with experiments. The reaction dynamics is also investigated with QCT on the new PES, which found that the reactivity is constrained by the entrance barriers and the final product branching is not statistical.

Authors:
ORCiD logo [1];  [2]; ORCiD logo [2]
  1. School of Chemistry and Chemical Engineering; Chongqing University; Chongqing 401331; China
  2. Department of Chemistry and Chemical Biology; University of New Mexico; Albuquerque; USA
Publication Date:
Research Org.:
Lawrence Berkeley National Laboratory-National Energy Research Scientific Computing Center
Sponsoring Org.:
USDOE
OSTI Identifier:
1492441
DOE Contract Number:  
SC0015997
Resource Type:
Journal Article
Journal Name:
Physical Chemistry Chemical Physics. PCCP (Print)
Additional Journal Information:
Journal Volume: 19; Journal Issue: 34; Journal ID: ISSN 1463-9076
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English

Citation Formats

Li, Jun, Xie, Changjian, and Guo, Hua. Kinetics and dynamics of the C(3P) + H2 O reaction on a full-dimensional accurate triplet state potential energy surface. United States: N. p., 2017. Web. doi:10.1039/c7cp04578f.
Li, Jun, Xie, Changjian, & Guo, Hua. Kinetics and dynamics of the C(3P) + H2 O reaction on a full-dimensional accurate triplet state potential energy surface. United States. doi:10.1039/c7cp04578f.
Li, Jun, Xie, Changjian, and Guo, Hua. Sun . "Kinetics and dynamics of the C(3P) + H2 O reaction on a full-dimensional accurate triplet state potential energy surface". United States. doi:10.1039/c7cp04578f.
@article{osti_1492441,
title = {Kinetics and dynamics of the C(3P) + H2 O reaction on a full-dimensional accurate triplet state potential energy surface},
author = {Li, Jun and Xie, Changjian and Guo, Hua},
abstractNote = {A full dimensional accurate potential energy surface (PES) for the C(3P) and H2O reaction is developed based on ~34 000 data points calculated at the level of the explicitly correlated unrestricted coupled cluster method with single, double, and perturbative triple excitations with the augmented correlation-consistent polarized triple zeta basis set (CCSD(T)-F12a/AVTZ). The PES is invariant with respect to the permutation of the two hydrogen atoms and the total root mean square error (RMSE) of the fit is only 0.31 kcal mol-1. The PES features two barriers in the entrance channel and several potential minima, as well as multiple product channels. The rate coefficients of this reaction calculated using a transition-state theory and quasi-classical trajectory (QCT) method are small near room temperature, consistent with experiments. The reaction dynamics is also investigated with QCT on the new PES, which found that the reactivity is constrained by the entrance barriers and the final product branching is not statistical.},
doi = {10.1039/c7cp04578f},
journal = {Physical Chemistry Chemical Physics. PCCP (Print)},
issn = {1463-9076},
number = 34,
volume = 19,
place = {United States},
year = {2017},
month = {1}
}

Works referenced in this record:

The Nature of the Chemical Bond. ii. the One-Electron bond and the Three-Electron bond
journal, September 1931

  • Pauling, Linus.
  • Journal of the American Chemical Society, Vol. 53, Issue 9
  • DOI: 10.1021/ja01360a004

A simple and efficient CCSD(T)-F12 approximation
journal, December 2007

  • Adler, Thomas B.; Knizia, Gerald; Werner, Hans-Joachim
  • The Journal of Chemical Physics, Vol. 127, Issue 22
  • DOI: 10.1063/1.2817618

Development of Accurate Quantum Dynamical Methods for Tetraatomic Reactions
journal, April 1997

  • Zhang, John Z. H.; Dai, Jiqiong; Zhu, Wei
  • The Journal of Physical Chemistry A, Vol. 101, Issue 15
  • DOI: 10.1021/jp9620734

Three-State Trajectory Surface Hopping Studies of the Photodissociation Dynamics of Formaldehyde on ab Initio Potential Energy Surfaces
journal, May 2011

  • Fu, Bina; Shepler, Benjamin C.; Bowman, Joel M.
  • Journal of the American Chemical Society, Vol. 133, Issue 20
  • DOI: 10.1021/ja201559r

Permutationally invariant potential energy surfaces in high dimensionality
journal, October 2009

  • Braams, Bastiaan J.; Bowman, Joel M.
  • International Reviews in Physical Chemistry, Vol. 28, Issue 4
  • DOI: 10.1080/01442350903234923

The unimolecular dissociation of HCO: I. Oscillations of pure CO stretching resonance widths
journal, March 1995

  • Werner, Hans‐Joachim; Bauer, Cornelia; Rosmus, Pavel
  • The Journal of Chemical Physics, Vol. 102, Issue 9
  • DOI: 10.1063/1.468588

Ab initio study of the addition of atomic carbon with water
journal, June 1999


A Global Potential Energy Surface Describing the N( 2 D) + H 2 O Reaction and a Quasiclassical Trajectory Study of the Reaction to NH + OH
journal, January 2014

  • Homayoon, Zahra; Bowman, Joel M.
  • The Journal of Physical Chemistry A, Vol. 118, Issue 3
  • DOI: 10.1021/jp410935k

High-dimensional ab initio potential energy surfaces for reaction dynamics calculations
journal, January 2011

  • Bowman, Joel M.; Czakó, Gábor; Fu, Bina
  • Physical Chemistry Chemical Physics, Vol. 13, Issue 18
  • DOI: 10.1039/c0cp02722g

Gaussian basis sets for use in correlated molecular calculations. I. The atoms boron through neon and hydrogen
journal, January 1989

  • Dunning, Thom H.
  • The Journal of Chemical Physics, Vol. 90, Issue 2
  • DOI: 10.1063/1.456153

Chemical Reaction Rate Coefficients from Ring Polymer Molecular Dynamics: Theory and Practical Applications
journal, September 2016

  • Suleimanov, Yury V.; Aoiz, F. Javier; Guo, Hua
  • The Journal of Physical Chemistry A, Vol. 120, Issue 43
  • DOI: 10.1021/acs.jpca.6b07140

Reactions of 1S, 1D, and 3P carbon atoms with water. Oxygen abstraction and intermolecular formaldehyde generation mechanisms; An MCSCF study
journal, May 2011

  • Ozkan, Ilker; Dede, Yavuz
  • International Journal of Quantum Chemistry, Vol. 112, Issue 4
  • DOI: 10.1002/qua.23103

Electron affinities of the first‐row atoms revisited. Systematic basis sets and wave functions
journal, May 1992

  • Kendall, Rick A.; Dunning, Thom H.; Harrison, Robert J.
  • The Journal of Chemical Physics, Vol. 96, Issue 9
  • DOI: 10.1063/1.462569

Reactions of atomic carbon with alcohols
journal, July 1969

  • Skell, Philip S.; Harris, Robert F.
  • Journal of the American Chemical Society, Vol. 91, Issue 16
  • DOI: 10.1021/ja01044a021

The Sudden Vector Projection Model for Reactivity: Mode Specificity and Bond Selectivity Made Simple
journal, October 2014

  • Guo, Hua; Jiang, Bin
  • Accounts of Chemical Research, Vol. 47, Issue 12
  • DOI: 10.1021/ar500350f

Quantum Tunneling Enhancement of the C + H 2 O and C + D 2 O Reactions at Low Temperature
journal, September 2016

  • Hickson, Kevin M.; Loison, Jean-Christophe; Nuñez-Reyes, Dianailys
  • The Journal of Physical Chemistry Letters, Vol. 7, Issue 18
  • DOI: 10.1021/acs.jpclett.6b01637

Permutationally Invariant Polynomial Basis for Molecular Energy Surface Fitting via Monomial Symmetrization
journal, November 2009

  • Xie, Zhen; Bowman, Joel M.
  • Journal of Chemical Theory and Computation, Vol. 6, Issue 1
  • DOI: 10.1021/ct9004917

Direct dynamics calculation of the kinetic isotope effect for an organic hydrogen-transfer reaction, including corner-cutting tunneling in 21 dimensions
journal, August 1993

  • Liu, Yi Ping; Lu, Da Hong; Gonzalez-Lafont, Angels
  • Journal of the American Chemical Society, Vol. 115, Issue 17
  • DOI: 10.1021/ja00070a029

Kinetic investigation of ground state carbon atoms, C(23 P J )
journal, January 1975

  • Husain, David; Young, Alan N.
  • Journal of the Chemical Society, Faraday Transactions 2, Vol. 71
  • DOI: 10.1039/f29757100525

A new set of potential energy surfaces for HCO: Influence of Renner-Teller coupling on the bound and resonance vibrational states
journal, June 2016

  • Ndengué, Steve Alexandre; Dawes, Richard; Guo, Hua
  • The Journal of Chemical Physics, Vol. 144, Issue 24
  • DOI: 10.1063/1.4954374

The unimolecular dissociation of H2CO on the lowest triplet potential-energy surface
journal, April 1998

  • Yamaguchi, Yukio; Wesolowski, Steven S.; Van Huis, Timothy J.
  • The Journal of Chemical Physics, Vol. 108, Issue 13
  • DOI: 10.1063/1.476315

Configuration interaction calculations on the nitrogen molecule
journal, January 1974

  • Langhoff, Stephen R.; Davidson, Ernest R.
  • International Journal of Quantum Chemistry, Vol. 8, Issue 1
  • DOI: 10.1002/qua.560080106

An experimental and ab initio study of the addition of atomic carbon to water
journal, June 1983

  • Ahmed, Sheikh N.; McKee, Michael L.; Shevlin, Philip B.
  • Journal of the American Chemical Society, Vol. 105, Issue 12
  • DOI: 10.1021/ja00350a033

Potential energy surfaces from high fidelity fitting of ab initio points: the permutation invariant polynomial - neural network approach
journal, July 2016


Training feedforward networks with the Marquardt algorithm
journal, January 1994

  • Hagan, M. T.; Menhaj, M. B.
  • IEEE Transactions on Neural Networks, Vol. 5, Issue 6
  • DOI: 10.1109/72.329697

Simplified CCSD(T)-F12 methods: Theory and benchmarks
journal, February 2009

  • Knizia, Gerald; Adler, Thomas B.; Werner, Hans-Joachim
  • The Journal of Chemical Physics, Vol. 130, Issue 5
  • DOI: 10.1063/1.3054300

Vectorization of the general Monte Carlo classical trajectory program VENUS
journal, October 1991

  • Hu, Xiche; Hase, William L.; Pirraglia, Tony
  • Journal of Computational Chemistry, Vol. 12, Issue 8
  • DOI: 10.1002/jcc.540120814

Quasi-classical trajectory studies on the full-dimensional accurate potential energy surface for the OH + H 2 O = H 2 O + OH reaction
journal, January 2017

  • Bai, Mengna; Lu, Dandan; Li, Jun
  • Physical Chemistry Chemical Physics, Vol. 19, Issue 27
  • DOI: 10.1039/C7CP02656K

Vibrational State Control of Bimolecular Reactions:  Discovering and Directing the Chemistry
journal, October 1999

  • Crim, F. Fleming
  • Accounts of Chemical Research, Vol. 32, Issue 10
  • DOI: 10.1021/ar950046a

Permutation invariant polynomial neural network approach to fitting potential energy surfaces
journal, August 2013

  • Jiang, Bin; Guo, Hua
  • The Journal of Chemical Physics, Vol. 139, Issue 5
  • DOI: 10.1063/1.4817187

A b i n i t i o calculations of electronic and vibrational energies of HCO and HOC
journal, July 1986

  • Bowman, Joel M.; Bittman, Joseph S.; Harding, Lawrence B.
  • The Journal of Chemical Physics, Vol. 85, Issue 2
  • DOI: 10.1063/1.451246

Communication: Covalent nature of X⋯H 2 O (X = F, Cl, and Br) interactions
journal, April 2013

  • Li, Jun; Li, Yongle; Guo, Hua
  • The Journal of Chemical Physics, Vol. 138, Issue 14
  • DOI: 10.1063/1.4801872

Quasiclassical Trajectory Calculations of the N( 2 D) + H 2 O Reaction Elucidating the Formation Mechanism of HNO and HON Seen in Molecular Beam Experiments
journal, September 2014

  • Homayoon, Zahra; Bowman, Joel M.; Balucani, Nadia
  • The Journal of Physical Chemistry Letters, Vol. 5, Issue 20
  • DOI: 10.1021/jz501757s

Quantum dynamics of complex-forming bimolecular reactions
journal, January 2012


Permutation invariant polynomial neural network approach to fitting potential energy surfaces. II. Four-atom systems
journal, November 2013

  • Li, Jun; Jiang, Bin; Guo, Hua
  • The Journal of Chemical Physics, Vol. 139, Issue 20
  • DOI: 10.1063/1.4832697

Insights into the bond-selective reaction of Cl + HOD(n OH ) → HCl + OD
journal, January 2015

  • Li, Jun; Song, Hongwei; Guo, Hua
  • Physical Chemistry Chemical Physics, Vol. 17, Issue 6
  • DOI: 10.1039/C4CP05165C

Reactions of carbon atoms/clusters with methane, methyl bromide, and water at 10 K and 77 K
journal, November 1989

  • Jeong, Gi Ho; Klabunde, Kenneth J.; Pan, Ohm Guo
  • Journal of the American Chemical Society, Vol. 111, Issue 24
  • DOI: 10.1021/ja00206a003

Reactions of small carbon clusters with water in cryogenic matrixes: the FTIR spectrum of hydroxyethynyl carbene
journal, October 1990

  • Ortman, Bryan J.; Hauge, Robert H.; Margrave, John L.
  • The Journal of Physical Chemistry, Vol. 94, Issue 20
  • DOI: 10.1021/j100383a041

Reactions of atomic carbon C(23 P J ) by kinetic absorption spectroscopy in the vacuum ultra-violet
journal, January 1971


Chemistry of Dark Clouds: Databases, Networks, and Models
journal, October 2013

  • Agúndez, Marcelino; Wakelam, Valentine
  • Chemical Reviews, Vol. 113, Issue 12
  • DOI: 10.1021/cr4001176

Variational Transition State Theory
journal, October 1984


Explicitly correlated multireference configuration interaction: MRCI-F12
journal, January 2011

  • Shiozaki, Toru; Knizia, Gerald; Werner, Hans-Joachim
  • The Journal of Chemical Physics, Vol. 134, Issue 3
  • DOI: 10.1063/1.3528720

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

  • Li, Jun; Jiang, Bin; Song, Hongwei
  • The Journal of Physical Chemistry A, Vol. 119, Issue 20
  • DOI: 10.1021/acs.jpca.5b02510

Variational reaction path algorithm
journal, September 1998

  • Fast, Patton L.; Truhlar, Donald G.
  • The Journal of Chemical Physics, Vol. 109, Issue 10
  • DOI: 10.1063/1.476973

An accurate multi-channel multi-reference full-dimensional global potential energy surface for the lowest triplet state of H 2 O 2
journal, January 2016

  • Li, Jun; Dawes, Richard; Guo, Hua
  • Physical Chemistry Chemical Physics, Vol. 18, Issue 43
  • DOI: 10.1039/C6CP06232F

Recent Advances in Quantum Dynamics of Bimolecular Reactions
journal, May 2016


The “Non-Reaction” of Ground-State Triplet Carbon Atoms with Water Revisited
journal, April 2006