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Title: Direct diabatization and analytic representation of coupled potential energy surfaces and couplings for the reactive quenching of the excited 2Σ+ state of OH by molecular hydrogen

Journal Article · · Journal of Chemical Physics
DOI: https://doi.org/10.1063/1.5111547 · OSTI ID:1612364
ORCiD logo [1];  [1]; ORCiD logo [2]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [3]; ORCiD logo [4]; ORCiD logo [1]
  1. Univ. of Minnesota, Minneapolis, MN (United States)
  2. Emory Univ., Atlanta, GA (United States); Univ. de São Paulo (Brazil)
  3. Emory Univ., Atlanta, GA (United States); Chinese Academy of Sciences, Dalian (People’s Republic of China)
  4. Emory Univ., Atlanta, GA (United States)
+ Show Author Affiliations

In this work, we have employed extended multiconfiguration quasidegenerate perturbation theory, fourfold-way diabatic molecular orbitals, and configurational uniformity to develop a global three-state diabatic representation of the potential energy surfaces and their couplings for the electronically nonadiabatic reaction OH* + H2 → H2O + H, where * denotes electronic excitation to the A 2Σ+ state. To achieve sign consistency of the computed diabatic couplings, we developed a graphics processing unit-accelerated algorithm called the cluster-growing algorithm. Having obtained consistent signs of the diabatic couplings, we fit the diabatic matrix elements (which consist of the diabatic potentials and the diabatic couplings) to analytic representations. Adiabatic potential energy surfaces are generated by diagonalizing the 3 × 3 diabatic potential energy matrix. The comparisons between the fitted and computed diabatic matrix elements and between the originally computed adiabatic potential energy surfaces and those generated from the fits indicate that the current fit is accurate enough for dynamical studies, and it may be used for quantal or semiclassical dynamics calculations.

Research Organization:
Univ. of New Mexico, Albuquerque, NM (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES); Coordenação de Aperfeiçoamento de Pessoal de Nível Superior-Brasil (CAPES); Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)
Grant/Contract Number:
SC0015997; 306830/2018-3; 421077/2018-2
OSTI ID:
1612364
Alternate ID(s):
OSTI ID: 1562133
Journal Information:
Journal of Chemical Physics, Vol. 151, Issue 10; ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)Copyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 25 works
Citation information provided by
Web of Science

References (97)

Direct calculation of coupled diabatic potential-energy surfaces for ammonia and mapping of a four-dimensional conical intersection seam journal March 2006
A novel Gaussian Binning (1GB) analysis of vibrational state distributions in highly excited H2O from reactive quenching of OH* by H2 journal July 2013
Diabatic bases and molecular properties journal January 2000
Adiabatic and diabatic potential energy surfaces for collisions of CN( X   2 Σ + ,  A   2 Π) with He journal September 1988
Approximately diabatic states from block diagonalization of the electronic Hamiltonian journal December 1988
Quasiclassical trajectory study of the postquenching dynamics of OH AΣ2+ by H2/D2 on a global potential energy surface journal October 2010
Diabatic Molecular Orbitals, Potential Energies, and Potential Energy Surface Couplings by the 4-fold Way for Photodissociation of Phenol journal July 2013
Quenching of OH (A2Σ+, ′=0) by several collision partners between 200 and 344 K. Cross-section measurements and model comparisons journal January 2000
Diabolical conical intersections journal October 1996
Permutationally invariant potential energy surfaces in high dimensionality journal October 2009
Role of Conical Intersections in Molecular Spectroscopy and Photoinduced Chemical Dynamics journal May 2012
Global ab initio ground-state potential energy surface of N 4 journal July 2013
An optimal adiabatic-to-diabatic transformation of the 1 2A′ and 2 2A′ states of H3 journal January 2002
Interpolation of multidimensional diabatic potential energy matrices journal September 2006
Reactive quenching of OH(AΣ+2) by D2 studied using crossed molecular beams journal May 2006
Understanding Nonradiative Recombination through Defect-Induced Conical Intersections journal August 2017
On the Construction of Property Based Diabatizations: Diabolical Singular Points journal October 2015
Probing reactive potential energy surfaces by vibrational activation of H 2 -OH entrance channel complexes journal October 2000
Dynamical Outcomes of Quenching: Reflections on a Conical Intersection journal April 2014
Molecular symmetry and spectroscopy journal October 1980
An improved potential energy surface and multi-temperature quasiclassical trajectory calculations of N 2 + N 2 dissociation reactions journal August 2015
Conical Intersections at the Nanoscale: Molecular Ideas for Materials journal June 2019
Revised M06 density functional for main-group and transition-metal chemistry journal September 2018
Quasi-diabatic states and dynamical couplings from ab initio CI calculations: a new proposal journal August 1985
A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu journal April 2010
Direct diabatization of electronic states by the fourfold way. II. Dynamical correlation and rearrangement processes journal September 2002
Ab initio potential-energy surfaces for the reactions OH+H2↔H2O+H journal July 2001
Modified Bond Eigenfunction Method of Constructing Potential Energy Surface of Reaction. II. Application to the Hydrogen Atom-Molecule Reaction journal October 1959
Effect of the damping function in dispersion corrected density functional theory journal March 2011
The interaction of OH( X 2 Π) with H 2 : Ab initio potential energy surfaces and bound states journal November 2014
Collisional quenching of OD AΣ2+ by H2: Experimental and theoretical studies of the state-resolved OD XΠ2 product distribution and branching fraction journal October 2010
Electronic Excitation: Nonadiabatic Transitions book January 1979
The role of conical intersections in the nonadiabatic quenching of OH(A 2Σ+) by molecular hydrogen journal December 2000
Convergence of molecular potential energy surfaces by interpolation: Application to the OH+H 2 →H 2 O+H reaction journal April 1995
Mode-selective decay dynamics of the ortho -H 2 —OH complex: experiment and theory journal July 1999
Determination of diabatic states through enforcement of configurational uniformity
  • Atchity, Gregory J.; Ruedenberg, Klaus
  • Theoretical Chemistry Accounts: Theory, Computation, and Modeling (Theoretica Chimica Acta), Vol. 97, Issue 1-4 https://doi.org/10.1007/s002140050236
journal October 1997
Extension of the fourfold way for calculation of global diabatic potential energy surfaces of complex, multiarrangement, non-Born–Oppenheimer systems: Application to HNCO(S0,S1) journal April 2003
Model space diabatization for quantum photochemistry journal February 2015
Learning to interpolate molecular potential energy surfaces with confidence: A Bayesian approach journal July 1999
Nonadiabatic effects in C–Br bond scission in the photodissociation of bromoacetyl chloride journal November 2006
Electronic spectrum and characterization of diabatic potential energy surfaces for thiophenol journal January 2018
Diabatization based on the dipole and quadrupole: The DQ method journal September 2014
Nonadiabatic quantum reactive scattering of the OH(A Σ2+)+D2 journal November 2010
Direct diabatization based on nonadiabatic couplings: the N/D method journal January 2018
Photodissociation Dynamics of Phenol: Multistate Trajectory Simulations including Tunneling journal November 2014
Efficient global representations of potential energy functions: Trajectory calculations of bimolecular gas-phase reactions by multiconfiguration molecular mechanics journal January 2009
Polyatomic molecular potential energy surfaces by interpolation in local internal coordinates journal May 1998
Analytic potential energy surfaces and their couplings for the electronically nonadiabatic chemical processes Na(3p)+H2→Na(3s)+H2 and Na(3p)+H2→NaH+H journal March 1999
The direct calculation of diabatic states based on configurational uniformity journal January 2001
A new diabatic representation of the coupled potential energy surfaces for Na(3 p 2 P )+H 2 →Na(3 s 2 S )+H 2 or NaH+H journal February 1992
Determining quasidiabatic coupled electronic state Hamiltonians using derivative couplings: A normal equations based method journal September 2008
Erratum: “Global ab initio ground-state potential energy surface of N 4 ” [J. Chem. Phys. 139, 044309 (2013)] journal January 2014
A global potential energy surface for the H 2 + OH ↔ H 2 O + H reaction using neural networks journal April 2013
Rotational-Level Dependence of OH A 2 Σ + Quenching at 242 and 196 K journal October 2002
A quantum chemical determination of diabatic states journal September 1993
Quasidegenerate perturbation theory with multiconfigurational self‐consistent‐field reference functions journal November 1993
Fitting coupled potential energy surfaces for large systems: Method and construction of a 3-state representation for phenol photodissociation in the full 33 internal degrees of freedom using multireference configuration interaction determined data journal January 2014
High-dimensional ab initio potential energy surfaces for reaction dynamics calculations journal January 2011
Gaussian basis sets for use in correlated molecular calculations. I. The atoms boron through neon and hydrogen journal January 1989
Molecular Symmetry and Spectroscopy journal August 1979
Electronic quenching of OH AΣ+2 radicals in single collision events with molecular hydrogen: Quantum state distribution of the OH XΠ2 products journal May 2007
Isomerization Through Conical Intersections journal May 2007
Product branching between reactive and nonreactive pathways in the collisional quenching of OH AΣ+2 radicals by H2 journal October 2007
Communications: Classical trajectory study of the postquenching dynamics of OH A ∑2+ by H2 initiated at conical intersections journal March 2010
Improved direct diabatization and coupled potential energy surfaces for the photodissociation of ammonia journal March 2007
Permutationally Invariant Polynomial Basis for Molecular Energy Surface Fitting via Monomial Symmetrization journal November 2009
Quenching of OH(A 2 Σ + ) by H 2 through Conical Intersections: Highly Excited Products in Nonreactive Channel journal June 2010
Full-dimensional potentials and state couplings and multidimensional tunneling calculations for the photodissociation of phenol journal January 2014
OH-H 2 ENTRANCE CHANNEL COMPLEXES journal October 1997
Nonadiabatic Events and Conical Intersections journal May 2011
Neural network diabatization: A new ansatz for accurate high-dimensional coupled potential energy surfaces journal November 2018
On the adiabatic to diabatic states transformation in the presence of a conical intersection: A most diabatic basis from the solution to a Poisson’s equation. I journal July 1998
Extended multi-configuration quasi-degenerate perturbation theory: The new approach to multi-state multi-reference perturbation theory journal June 2011
The ’’noncrossing’’ rule for electronic potential energy surfaces: The role of time‐reversal invariance journal March 1979
Accurate ab initio potential energy curve of O2. II. Core-valence correlations, relativistic contributions, and vibration-rotation spectrum journal February 2010
Reactive Quenching of OH A 2 Σ + in Collisions with Molecular Deuterium via Nonadiabatic Passage through a Conical Intersection journal November 2001
Deazaflavin reductive photocatalysis involves excited semiquinone radicals text January 2020
Properties of nonadiabatic couplings and the generalized Born–Oppenheimer approximation journal March 2002
Electronic quenching of OH A2Σ+ radicals in collisions with molecular hydrogen journal April 2006
Full-dimensional ground- and excited-state potential energy surfaces and state couplings for photodissociation of thioanisole journal February 2017
The DQ and DQΦ electronic structure diabatization methods: Validation for general applications journal May 2016
Reactive quenching of electronically excited OH radicals in collisions with molecular hydrogen journal June 1999
On the mechanism for the nonadiabatic reactive quenching of OH(A 2 Σ + ) by H 2 ( 1 Σg+): The role of the 2 2 A state journal August 2013
Intruder state avoidance multireference Møller-Plesset perturbation theory: Multireference Møller-Plesset Perturbation Theory journal May 2002
On the effects of spin–orbit coupling on conical intersection seams in molecules with an odd number of electrons. II. Characterizing the local topography of the seam journal September 2001
Molecular Symmetry and Spectroscopy journal June 1980
No equatorial divide for a cleansing radical journal September 2014
Collisional quenching of high rotational levels in A 2Σ+ OH journal August 2001
The use of effective Hamiltonians for the treatment of avoided crossings. II. Nearly diabatic potential curves journal April 1984
Electronic Quenching of OH A 2 Σ + ( v ‘ = 0, 1) in Complexes with Hydrogen and Nitrogen journal December 1997
Quasi diabatic CASSCF state functions journal March 2002
Direct diabatization of electronic states by the fourfold-way: Including dynamical correlation by multi-configuration quasidegenerate perturbation theory with complete active space self-consistent-field diabatic molecular orbitals journal June 2013
MCSCF optimization through combined use of natural orbitals and the brillouin-levy-berthier theorem journal November 1979
Research activities of the theoretical chemistry group at the University of Tokyo journal October 2001
An ab initio quasi-diabatic potential energy matrix for OH( 2 Σ) + H 2 journal December 2011
Multireference Model Chemistries for Thermochemical Kinetics journal July 2008
Seams of Conical Intersections Relevant to the Quenching of OH(A 2 Σ + ) by Collisions with H 2 journal April 2013

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Chemistry
Physics
Diabatization
Potential energy surfaces
Electronic excitation
Excitation energies
Perturbation theory
Graphics processing units