Full-dimensional quantum mechanical calculation of the rate constant for the H2+OH→H2O+H reaction

Manthe, Uwe; Seideman, Tamar; Miller, William H.

doi:10.1063/1.465514

Cited by 195 publications

(136 citation statements)

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“…After the geometry of the SVRT molecule is fixed, the TD dynamics calculation is carried out on this reduced 4D potential. The basis functions used is similar to that for HϩCH 4 . 21 The only difference is that the maximum rotational quantum state of the CH x D y molecule included in the basis expansion is j max ϭ38 which is sufficient to give a converged result.…”

Section: Resultsmentioning

confidence: 99%

“…21. This paper is organized as follows: Section II gives a brief review of the mathematical treatment of the SVRT model for atompolyatomic reactions with specific application to the HϩCD 4 and HϩCHD 3 reactions. The result of numerical calculation and discussions are given in Sec.…”

Section: ͑1͒mentioning

confidence: 99%

“…For reactions beyond tetratomic systems, [1][2][3][4][5][6][7][8][9] it is essential to reduce the number of mathematical dimensions in quantum dynamics calculations. [10][11][12][13][14][15][16] Recently, the SVRT ͑semirigid vibrating rotor target͒ method was proposed as a general theoretical model, albeit approximate, to study polyatomic reaction dynamics.…”

Section: Introductionmentioning

confidence: 99%

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Quantum dynamics study of isotope effect for H+CH4 reaction using the SVRT model

Zhang

Yang

Han

et al. 2003

The Journal of Chemical Physics

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The semirigid vibrating rotor target model is applied to study the isotope effect in reaction HϩCH 4 →H 2 ϩCH 3 using time-dependent wave-packet method. The reaction probabilities for producing H 2 and HD product channels are calculated. The energy dependence of the reaction probabilities shows oscillating structures for both reaction channels. At low temperature or collision energies, the H atom abstraction is favored due to tunnelling effect. In partially deuterated CH x D y (xϩyϭ4), the breaking of the C-H bond is favored over that of the C-D bond in the entire energy range studied. In HϩCHD 3 reaction at high energies, the HD product dominates simply due to statistical factor.

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Section: Resultsmentioning

confidence: 99%

Section: ͑1͒mentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Quantum dynamics study of isotope effect for H+CH4 reaction using the SVRT model

Zhang

Yang

Han

et al. 2003

The Journal of Chemical Physics

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“…Despite this, GMRES has been used successfully in some cases. 3,[28][29][30] Other methods which have been applied successfully are the quasi-minimum residual ͑QMR͒, 31,32 and complex-symmetric Lanczos algorithms. [33][34][35][36] These methods require less storage, but are not as rapidly convergent as GMRES.…”

Section: ͑2͒mentioning

confidence: 99%

The simulation of outgoing-wave boundary conditions via a symmetrically damped, Hermitian Hamiltonian operator

Smith

1997

The Journal of Chemical Physics

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Articles you may be interested inA MATLAB-based finite-element visualization of quantum reactive scattering. I. Collinear atom-diatom reactions J. Chem. Phys. 141, 024118 (2014) A new method for simulating the effect of outgoing-wave boundary conditions in the calculation of quantum resonances is presented. The Hermitian Hamiltonian operator H is multiplied on each side by a damping operator D, consisting of a real function d(R), which is unity in the resonance region and falls gradually to zero in the asymptotic region. The spectrum of the symmetrically damped Hamiltonian operator, DHD is shown to provide an excellent approximation to the resonance energies of the Hamiltonian with outgoing-wave boundary conditions. Applications to the calculation of resonance energies for collinear HϩH 2 scattering and for HO 2 dissociation are presented. In addition, we explore the feasibility of extracting resonance widths by using the DHD operator within a filter diagonalization ͑FD͒ scheme. Application of the FD scheme to HO 2 yields encouraging results.

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“…One advantage of this formulation is that the variational principle is used to identify the relevant subspace of the basis set. This approach is appealing in terms of its generality and straightforward extension to larger systems, and it is extended to polyatomic reactions in this article.In this work, we have used flux autocorrelation functions to compute the thermal rate constants of two benchmark reactions: collinear H ϩ H 2 3H 2 ϩ H (which is used as a test of our computer program) and full-dimensional OH ϩ H 2 3H 2 O ϩ H. Both of these reactions have been studied extensively in the past by using various potential energy surfaces (8,11,13,16,20,(22)(23)(24)(25)(26)(27)(28)(29)(30)(31)(32)(33)(34)(35)(36)(37), although most calculations involve approximations in the dynamics. In this work, we have used a time-independent square-integrable (L 2 ) basis set to represent the Hamiltonian and the flux operator, and we formulated the method in a way that should be applicable to general polyatomic reactions.…”

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confidence: 99%

Quantum mechanical reaction rate constants by vibrational configuration interaction: The OH + H₂→H₂O + H reaction as a function of temperature

Chakraborty

Truhlar

2005

Proc. Natl. Acad. Sci. U.S.A.

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The thermal rate constant of the 3D OH ؉ H23 H2O ؉ H reaction was computed by using the flux autocorrelation function, with a time-independent square-integrable basis set. Two modes that actively participate in bond making and bond breaking were treated by using 2D distributed Gaussian functions, and the remaining (nonreactive) modes were treated by using harmonic oscillator functions. The finite-basis eigenvalues and eigenvectors of the Hamiltonian were obtained by solving the resulting generalized eigenvalue equation, and the flux autocorrelation function for a dividing surface optimized in reduced-dimensionality calculations was represented in the basis formed by the eigenvectors of the Hamiltonian. The rate constant was obtained by integrating the flux autocorrelation function. The choice of the final time to which the integration is carried was determined by a plateau criterion. The potential energy surface was from Wu, Schatz, Lendvay, Fang, and Harding (WSLFH). We also studied the collinear H ؉ H2 reaction by using the Liu-Siegbahn-Truhlar-Horowitz (LSTH) potential energy surface. The calculated thermal rate constant results were compared with reported values on the same surfaces. The success of these calculations demonstrates that time-independent vibrational configuration interaction can be a very convenient way to calculate converged quantum mechanical rate constants, and it opens the possibility of calculating converged rate constants for much larger reactions than have been treated until now.flux autocorrelation ͉ chemical kinetics ͉ dynamics ͉ localized basis functions ͉ many-body problem T he evaluation of the thermal reaction rate constant k(T) from the quantum mechanical flux provides an efficient alternative to the computation of rate constants by means of the scattering matrix. The quantum mechanical formulation of k(T) in terms of flux autocorrelation functions C f (t) was presented by Yamamoto (1) and Miller et al. (2,3), and there have been several applications to calculate thermal rate constants for specific systems. The flux operator can be used to compute the cumulative reaction probability N(E) or the flux autocorrelation function, and either of these functions can be used to compute the thermal rate constant. Various approaches (4-24) involving basis functions, path integrals, and wave packet propagation methods have been used. Recently, Manthe and coworkers (19,22) have calculated the thermal rate constants for the CH 4 ϩ H3CH 3 ϩ H 2 and CH 4 ϩ O3CH 3 ϩ OH reactions by calculating N(E) as a function of energy E by using the multiconfiguration time-dependent Hartree (MCTDH) method. Earlier work on triatomic reactions showed that accurate results can be obtained with an approach based on diagonalizing the time-independent Hamiltonian (4, 8, 10). One advantage of this formulation is that the variational principle is used to identify the relevant subspace of the basis set. This approach is appealing in terms of its generality and straightforward extension to larger systems, and it is exte...

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Full-dimensional quantum mechanical calculation of the rate constant for the H2+OH→H2O+H reaction

Cited by 195 publications

References 35 publications

Quantum dynamics study of isotope effect for H+CH4 reaction using the SVRT model

Quantum dynamics study of isotope effect for H+CH4 reaction using the SVRT model

The simulation of outgoing-wave boundary conditions via a symmetrically damped, Hermitian Hamiltonian operator

Quantum mechanical reaction rate constants by vibrational configuration interaction: The OH + H₂→H₂O + H reaction as a function of temperature

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Full-dimensional quantum mechanical calculation of the rate constant for the H2+OH→H2O+H reaction

Cited by 195 publications

References 35 publications

Quantum dynamics study of isotope effect for H+CH4 reaction using the SVRT model

Quantum dynamics study of isotope effect for H+CH4 reaction using the SVRT model

The simulation of outgoing-wave boundary conditions via a symmetrically damped, Hermitian Hamiltonian operator

Quantum mechanical reaction rate constants by vibrational configuration interaction: The OH + H2→H2O + H reaction as a function of temperature

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Quantum mechanical reaction rate constants by vibrational configuration interaction: The OH + H₂→H₂O + H reaction as a function of temperature