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

This content will become publicly available on June 11, 2020

Title: An ab initio based full-dimensional potential energy surface for OH + O 2 ⮂ HO 3 and low-lying vibrational levels of HO 3

Abstract

To offer an in-depth understanding of the HO 3 radical and its dissociation to OH + O 2, a six-dimensional potential energy surface (PES) has been constructed by fitting 2087 energy points for the electronic ground state of HO 3 (X 2A") using the permutation invariant polynomial-neural network (PIP-NN) approach. The energy points were calculated using an explicitly-correlated and Davidson-corrected multi-reference configuration interaction approach with the correlation-consistent polarized valence double zeta basis (MRCI( Q)-F12/VDZ-F12). On the PES, the trans-HO 3 isomer is found to be the global minimum, 33.0 cm -1 below the cis-HO 3 conformer, which is consistent with previous high-level theoretical investigations. The dissociation to the OH + O 2 asymptote from both conformers is shown to be barrierless. As a benchmark from a recently developed high-accuracy thermochemistry protocol, D 0 for trans-HO 3 is calculated to be 2.29 ± 0.36 kcal mol -1, only slightly deeper than the value of 2.08 kcal mol -1 obtained using the PES, and in reasonable agreement with the experimentally estimated value of 2.93 ± 0.07 kcal mol -1. Using this PES, low-lying vibrational energy levels of HO 3 are determined using an exact quantum Hamiltonian and compared with available experimental results.

Authors:
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [3]; ORCiD logo [4]; ORCiD logo [3]; ORCiD logo [2]
  1. Nanjing Univ. (China); Univ. of New Mexico, Albuquerque, NM (United States)
  2. Nanjing Univ. (China)
  3. Univ. of New Mexico, Albuquerque, NM (United States)
  4. Missouri Univ. of Science and Technology, Rolla, MO (United States)
Publication Date:
Research Org.:
Univ. of New Mexico, Albuquerque, NM (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division; National Natural Science Foundation of China (NNSFC); National Science Foundation (NSF)
OSTI Identifier:
1598426
Alternate Identifier(s):
OSTI ID: 1526774
Grant/Contract Number:  
SC0015997; CHE-1566246
Resource Type:
Accepted Manuscript
Journal Name:
Physical Chemistry Chemical Physics. PCCP (Print)
Additional Journal Information:
Journal Name: Physical Chemistry Chemical Physics. PCCP (Print); Journal Volume: 21; Journal Issue: 25; Journal ID: ISSN 1463-9076
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Hu, Xixi, Zuo, Junxiang, Xie, Changjian, Dawes, Richard, Guo, Hua, and Xie, Daiqian. An ab initio based full-dimensional potential energy surface for OH + O2 ⮂ HO3 and low-lying vibrational levels of HO3. United States: N. p., 2019. Web. doi:10.1039/C9CP02206F.
Hu, Xixi, Zuo, Junxiang, Xie, Changjian, Dawes, Richard, Guo, Hua, & Xie, Daiqian. An ab initio based full-dimensional potential energy surface for OH + O2 ⮂ HO3 and low-lying vibrational levels of HO3. United States. doi:10.1039/C9CP02206F.
Hu, Xixi, Zuo, Junxiang, Xie, Changjian, Dawes, Richard, Guo, Hua, and Xie, Daiqian. Tue . "An ab initio based full-dimensional potential energy surface for OH + O2 ⮂ HO3 and low-lying vibrational levels of HO3". United States. doi:10.1039/C9CP02206F.
@article{osti_1598426,
title = {An ab initio based full-dimensional potential energy surface for OH + O2 ⮂ HO3 and low-lying vibrational levels of HO3},
author = {Hu, Xixi and Zuo, Junxiang and Xie, Changjian and Dawes, Richard and Guo, Hua and Xie, Daiqian},
abstractNote = {To offer an in-depth understanding of the HO3 radical and its dissociation to OH + O2, a six-dimensional potential energy surface (PES) has been constructed by fitting 2087 energy points for the electronic ground state of HO3 (X2A") using the permutation invariant polynomial-neural network (PIP-NN) approach. The energy points were calculated using an explicitly-correlated and Davidson-corrected multi-reference configuration interaction approach with the correlation-consistent polarized valence double zeta basis (MRCI(Q)-F12/VDZ-F12). On the PES, the trans-HO3 isomer is found to be the global minimum, 33.0 cm-1 below the cis-HO3 conformer, which is consistent with previous high-level theoretical investigations. The dissociation to the OH + O2 asymptote from both conformers is shown to be barrierless. As a benchmark from a recently developed high-accuracy thermochemistry protocol, D0 for trans-HO3 is calculated to be 2.29 ± 0.36 kcal mol-1, only slightly deeper than the value of 2.08 kcal mol-1 obtained using the PES, and in reasonable agreement with the experimentally estimated value of 2.93 ± 0.07 kcal mol-1. Using this PES, low-lying vibrational energy levels of HO3 are determined using an exact quantum Hamiltonian and compared with available experimental results.},
doi = {10.1039/C9CP02206F},
journal = {Physical Chemistry Chemical Physics. PCCP (Print)},
number = 25,
volume = 21,
place = {United States},
year = {2019},
month = {6}
}

Journal Article:
Free Publicly Available Full Text
This content will become publicly available on June 11, 2020
Publisher's Version of Record

Save / Share:

Works referenced in this record:

Oxygen-18 Isotopic Studies of HOOO and DOOO
journal, August 2017

  • Barreau, Lou; Martinez, Oscar; Crabtree, Kyle N.
  • The Journal of Physical Chemistry A, Vol. 121, Issue 33
  • DOI: 10.1021/acs.jpca.7b05380

Potential energy surface and quantum dynamics study of rovibrational states for HO3 (X 2A″)
journal, January 2008

  • Braams, Bastiaan J.; Yu, Hua-Gen
  • Physical Chemistry Chemical Physics, Vol. 10, Issue 21
  • DOI: 10.1039/b801928b

Communication: An accurate global potential energy surface for the ground electronic state of ozone
journal, November 2013

  • Dawes, Richard; Lolur, Phalgun; Li, Anyang
  • The Journal of Chemical Physics, Vol. 139, Issue 20
  • DOI: 10.1063/1.4837175

Weakly Bound Molecules in the Atmosphere: A Case Study of HOOO
journal, March 2009

  • Murray, Craig; Derro, Erika L.; Sechler, Timothy D.
  • Accounts of Chemical Research, Vol. 42, Issue 3
  • DOI: 10.1021/ar8001987

Communication: Highly accurate ozone formation potential and implications for kinetics
journal, August 2011

  • Dawes, Richard; Lolur, Phalgun; Ma, Jianyi
  • The Journal of Chemical Physics, Vol. 135, Issue 8
  • DOI: 10.1063/1.3632055

The Thermodynamics of the Elusive HO3 Radical
journal, June 2010


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

Complete basis set and density functional determination of the enthalpy of formation of the controversial HO3 radical: a discrepancy between theory and experiment
journal, November 2002


W4-11: A high-confidence benchmark dataset for computational thermochemistry derived from first-principles W4 data
journal, July 2011


On the Dissociation of Ground State trans -HOOO Radical: A Theoretical Study
journal, August 2010

  • Anglada, Josep M.; Olivella, Santiago; Solé, Albert
  • Journal of Chemical Theory and Computation, Vol. 6, Issue 9
  • DOI: 10.1021/ct100358e

Analysis of the HOOO torsional potential
journal, January 2011

  • Beames, Joseph M.; Lester, Marsha I.; Murray, Craig
  • The Journal of Chemical Physics, Vol. 134, Issue 4
  • DOI: 10.1063/1.3518415

Odd-hydrogen: An account on electronic structure, kinetics, and role of water in mediating reactions with atmospheric ozone. Just a catalyst or far beyond?
journal, November 2013

  • Varandas, António J. C.
  • International Journal of Quantum Chemistry, Vol. 114, Issue 20
  • DOI: 10.1002/qua.24580

Low temperature kinetics: the association of OH radicals with O2
journal, January 2010

  • Tizniti, Meryem; Le Picard, Sébastien D.; Canosa, André
  • Physical Chemistry Chemical Physics, Vol. 12, Issue 39
  • DOI: 10.1039/c0cp00591f

An Automated Thermochemistry Protocol Based on Explicitly Correlated Coupled-Cluster Theory: The Methyl and Ethyl Peroxy Families
journal, June 2019

  • Welch, Bradley K.; Dawes, Richard; Bross, David H.
  • The Journal of Physical Chemistry A, Vol. 123, Issue 26
  • DOI: 10.1021/acs.jpca.9b04381

Dynamically weighted multiconfiguration self-consistent field: Multistate calculations for F+H2O→HF+OH reaction paths
journal, April 2004

  • Deskevich, Michael P.; Nesbitt, David J.; Werner, Hans-Joachim
  • The Journal of Chemical Physics, Vol. 120, Issue 16
  • DOI: 10.1063/1.1667468

Comprehensive H2/O2 kinetic model for high-pressure combustion
journal, December 2011

  • Burke, Michael P.; Chaos, Marcos; Ju, Yiguang
  • International Journal of Chemical Kinetics, Vol. 44, Issue 7
  • DOI: 10.1002/kin.20603

On the molecular structure of HOOO
journal, January 2012

  • McCarthy, Michael C.; Lattanzi, Valerio; Kokkin, Damian
  • The Journal of Chemical Physics, Vol. 136, Issue 3
  • DOI: 10.1063/1.3673875

Infrared spectroscopy of HOOO and DOOO in 4 He nanodroplets
journal, November 2012

  • Raston, Paul L.; Liang, Tao; Douberly, Gary E.
  • The Journal of Chemical Physics, Vol. 137, Issue 18
  • DOI: 10.1063/1.4764298

Four-atom bimolecular reactions with relevance in environmental chemistry: Theoretical work
journal, April 2000


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

Theoretical study of the H+O 3 ↔OH+O 2 ↔O+HO 2 system
journal, March 1986

  • Dupuis, M.; Fitzgerald, G.; Hammond, B.
  • The Journal of Chemical Physics, Vol. 84, Issue 5
  • DOI: 10.1063/1.450342

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


Is HO3 minimum cis or trans? An analytic full-dimensional ab initio isomerization path
journal, January 2011

  • Varandas, A. J. C.
  • Physical Chemistry Chemical Physics, Vol. 13, Issue 20
  • DOI: 10.1039/c1cp20221a

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

Infrared Action Spectroscopy and Dissociation Dynamics of the HOOO Radical
journal, November 2007

  • Derro, Erika L.; Murray, Craig; Sechler, Timothy D.
  • The Journal of Physical Chemistry A, Vol. 111, Issue 45
  • DOI: 10.1021/jp0760915

Evolution of quantum system in order domain of Chebyshev operator
journal, September 1996

  • Chen, Rongqing; Guo, Hua
  • The Journal of Chemical Physics, Vol. 105, Issue 9
  • DOI: 10.1063/1.472228

Theoretical Characterization of Hydrogen Polyoxides: HOOH, HOOOH, HOOOOH, and HOOO
journal, January 2009

  • Denis, Pablo A.; Ornellas, Fernando R.
  • The Journal of Physical Chemistry A, Vol. 113, Issue 2
  • DOI: 10.1021/jp808795e

Dissociation Energy of the HOOO Radical
journal, October 2009

  • Varner, Mychel E.; Harding, Michael E.; Vázquez, Juana
  • The Journal of Physical Chemistry A, Vol. 113, Issue 42
  • DOI: 10.1021/jp907262s

Multireference explicitly correlated F12 theories
journal, March 2013


A new local density functional for main-group thermochemistry, transition metal bonding, thermochemical kinetics, and noncovalent interactions
journal, November 2006

  • Zhao, Yan; Truhlar, Donald G.
  • The Journal of Chemical Physics, Vol. 125, Issue 19, Article No. 194101
  • DOI: 10.1063/1.2370993

Dipole Moment of the HOOO Radical: Resolution of a Structural Enigma
journal, October 2013

  • Liang, Tao; Magers, D. Brandon; Raston, Paul L.
  • The Journal of Physical Chemistry Letters, Vol. 4, Issue 21
  • DOI: 10.1021/jz401927b

Double many-body expansion potential energy surface for ground-state HO 3
journal, June 1997


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

The Rotational Spectrum and Structure of the HOOO Radical
journal, June 2005


Ab Initio Treatment of Bond-Breaking Reactions: Accurate Course of HO 3 Dissociation and Revisit to Isomerization
journal, January 2012

  • Varandas, A. J. C.
  • Journal of Chemical Theory and Computation, Vol. 8, Issue 2
  • DOI: 10.1021/ct200773b

Ab initio study of the elusive HO3(X2A″) radical and the reaction
journal, December 2013


A Theoretical Study of the Potential Energy Surface and Rate Constant for an O( 3 P) + HO 2 Reaction
journal, April 2000

  • Setokuchi, Osamu; Sato, Masaru; Matuzawa, Sadao
  • The Journal of Physical Chemistry A, Vol. 104, Issue 14
  • DOI: 10.1021/jp993573a

Experimental Detection of Tetranitrogen
journal, January 2002


Systematically convergent basis sets for explicitly correlated wavefunctions: The atoms H, He, B–Ne, and Al–Ar
journal, February 2008

  • Peterson, Kirk A.; Adler, Thomas B.; Werner, Hans-Joachim
  • The Journal of Chemical Physics, Vol. 128, Issue 8
  • DOI: 10.1063/1.2831537

Observation of ν1+νn combination bands of the HOOO and DOOO radicals using infrared action spectroscopy
journal, June 2008

  • Derro, Erika L.; Sechler, Timothy D.; Murray, Craig
  • The Journal of Chemical Physics, Vol. 128, Issue 24
  • DOI: 10.1063/1.2945872

Multireference Character for 3d Transition-Metal-Containing Molecules
journal, January 2012

  • Jiang, Wanyi; DeYonker, Nathan J.; Wilson, Angela K.
  • Journal of Chemical Theory and Computation, Vol. 8, Issue 2
  • DOI: 10.1021/ct2006852

Weakly Bound Clusters in Astrochemistry? Millimeter and Submillimeter Spectroscopy of trans -HO 3 and Comparison to Astronomical Observations
journal, December 2015

  • Zou, Luyao; Hays, Brian M.; Weaver, Susanna L. Widicus
  • The Journal of Physical Chemistry A, Vol. 120, Issue 5
  • DOI: 10.1021/acs.jpca.5b09624

On the geometry of the HO3 radical
journal, May 2008


Six-dimensional quantum calculations of highly excited vibrational energy levels of hydrogen peroxide and its deuterated isotopomers
journal, March 2001

  • Chen, Rongqing; Ma, Guobin; Guo, Hua
  • The Journal of Chemical Physics, Vol. 114, Issue 11
  • DOI: 10.1063/1.1348274

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

Stability of the Hydrogen Trioxy Radical via Infrared Action Spectroscopy
journal, June 2007

  • Murray, Craig; Derro, Erika L.; Sechler, Timothy D.
  • The Journal of Physical Chemistry A, Vol. 111, Issue 22
  • DOI: 10.1021/jp071473w

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

  • Suma, Kohsuke; Sumiyoshi, Yoshihiro; Endo, Yasuki
  • The Journal of Chemical Physics, Vol. 139, Issue 9
  • DOI: 10.1063/1.4819323

Infrared Action Spectroscopy of the OD Stretch Fundamental and Overtone Transitions of the DOOO Radical
journal, October 2008

  • Derro, Erika L.; Sechler, Timothy D.; Murray, Craig
  • The Journal of Physical Chemistry A, Vol. 112, Issue 39
  • DOI: 10.1021/jp801232a

Theoretical and Experimental Spectroscopy of the S 2 State of CHF and CDF: Dynamically Weighted Multireference Configuration Interaction Calculations for High-Lying Electronic States
journal, January 2010

  • Dawes, Richard; Jasper, Ahren W.; Tao, Chong
  • The Journal of Physical Chemistry Letters, Vol. 1, Issue 3
  • DOI: 10.1021/jz900380a