Time-dependent quantum study of H(2S) + FO(2Pi) -> OH(2Pi) + F(2P) reaction on the 13A' and 13A" states (original) (raw)
Related papers
Time-dependent quantum study of H(2S) + FO(2Π) → OH(2Π) + F(2P) reaction on the 13A′ and 13A″ states
Journal of Computational Chemistry, 2010
The dynamics of the H( 2 S)+FO( 2 ) → OH( 2 )+F( 2 P) reaction on the adiabatic potential energy surface of the 1 3 A and 1 3 A states is investigated. The initial state selected reaction probabilities for total angular momentum J = 0 have been calculated by using the quantum mechanical real wave packet method. The integral cross sections and initial state selected reaction rate constants have been obtained from the corresponding J = 0 reaction probabilities by means of the simple J-Shifting technique. The initial state-selected reaction probabilities and reaction cross section do not manifest any sharp oscillations and the initial state selected reaction rate constants are sensitive to the temperature.
Quantum dynamics of reaction on the state
Molecular Physics, 2011
The Hð 2 SÞ þ FOð 2 ÅÞ ! HFð 1 AE þ Þ þ Oð 3 PÞ reaction on the 1 3 A 0 state potential energy surface is investigated using the quantum mechanical real wave packet method. The state-to-state and state-to-all reaction probabilities for total angular momentum J ¼ 0 have been calculated. The probabilities for J40 have been calculated by means of the simple J-shifting method. The initial state selected integral cross-sections and rate coefficients have been calculated. The state-to-state, state-to-all reaction probabilities and the reaction cross-section do not manifest any significant oscillations and the initial state selected reaction rate constants are sensitive to the temperature.
Real wave packet and flux analysis studies of the H + F2 → HF + F reaction
2012
The H + F 2 → HF + F reaction on ground state potential energy surface is investigated using the quantum mechanical real wave packet and Flux analysis method based on centrifugal sudden approximation. The initial state selected reaction probabilities for total angular momentum J = 0 have been calculated by both methods while the probabilities for J > 0 have been calculated by Flux analysis method. The initial state selected reaction probabilities, integral cross sections and rate coefficients have been calculated for a broad range of collision energy. The results
Full‐dimensional quantum mechanical calculation of the rate constant for the H2+OH→H2O+H reaction
The Journal of Chemical Physics, 1993
The cumulative reaction probability (CRP) (the Boltzmann average of which is the thermal rate constant) has been calculated for the reaction H,+OH++HzO+H in its full (six) dimensionality for total angular momentum J=O. The calculation, which should be the (numerically) exact result for the assumed potential energy surface, was carried out by a direct procedure that avoids having to solve the complete state-to-state reactive scattering problem. Higher angular momenta (J> 0) were taken into account approximately to obtain the thermal rate constant k(T) over the range 300 < T < 700 K; the result is significantly larger than the experimental values (a factor of-4 at 300 K), indicating that a more accurate potential energy surface is needed in order to provide a quantitative description of this reaction.
The Journal of Chemical Physics, 2003
In this paper we present a time-dependent quantum wave packet calculation for the reaction of F( 2 P 3/2 , 2 P 1/2 )ϩH 2 on the Alexander-Stark-Werner potential energy surface. The reaction probabilities and the integral cross sections for the reaction of F( 2 P 3/2 , 2 P 1/2 )ϩH 2 (vϭ jϭ0) are computed using time-dependent quantum methods with the centrifugal sudden approximate. The results are compared with recent time-independent quantum calculations. The two-surface reaction probability for the initial ground spin-orbit state of Jϭ0.5 is similar to the time-independent result obtained by Alexander et al. ͓J. Chem. Phys. 113, 11084 ͑2000͔͒. Our calculation also shows that electronic coupling has a relatively minor effect on the reactivity from the 2 P 3/2 state but a non-negligible one from the 2 P 1/2 state. By comparison with exact time-independent calculations, it is found that the Coriolis coupling plays a relatively minor role. In addition, most of the reactivity of the excited state of fluorine atom results from the spin-orbit coupling.
Seven dimensional quantum dynamics study of the H[sub 2]+NH[sub 2]→H+NH[sub 3] reaction
The Journal of Chemical Physics, 2007
Initial state-selected time-dependent wave packet dynamics calculations have been performed for the H 2 +NH 2 → H+NH 3 reaction using a seven dimensional model on an analytical potential energy surface based on the one developed by Corchado and Espinosa-García ͓J. Chem. Phys. 106, 4013 ͑1997͔͒. The model assumes that the two spectator NH bonds are fixed at their equilibrium values and nonreactive NH 2 group keeps C 2v symmetry and the rotation-vibration coupling in NH 2 is neglected. The total reaction probabilities are calculated when the two reactants are initially at their ground states, when the NH 2 bending mode is excited, and when H 2 is on its first vibrational excited state, with total angular momentum J = 0. The converged cross sections for the reaction are also reported for these initial states. Thermal rate constants and equilibrium constants are calculated for the temperature range of 200-2000 K and compared with transition state theory results and the available experimental data. The study shows that ͑a͒ the reaction is dominated by ground-state reactivity and the main contribution to the thermal rate constants is thought to come from this state, ͑b͒ the excitation energy of H 2 was used to enhance reactivity while the excitation of the NH 2 bending mode hampers the reaction, ͑c͒ the calculated thermal rate constants are very close to the experimental data and transition state theory results at high and middle temperature, while they are ten times higher than that of transition state theory at low temperature ͑T = 200 K͒, and ͑d͒ the equilibrium constants results indicate that the approximations applied may have different roles in the forward and reverse reactions. j tot MK ͑R ,r,ŝ͒ = ͱ 1 2͑1 + ␦ K 0 ␦ k0 ͒ ͓⌽ j 12 j 1 j 2 k 2 J tot MK ͑R ,r,ŝ͒ + p͑− 1͒ J tot +j 12 +j 1 +j 2 +k 2 ⌽ j 12 j 1 j 2 −k 1 J tot M−K ͑R ,r,ŝ͔͒,
A Quantum Wave Packet Dynamics Study of the N( 2 D) + H 2 Reaction †
The Journal of Physical Chemistry A, 2006
We report a dynamics study of the reaction N( 2 D) + H 2 (V)0, j)0-5) f NH + H using the time-dependent quantum wave packet method and a recently reported single-sheeted double many-body expansion potential energy surface for NH 2 (1 2 A′′) which has been modeled from accurate ab initio multireference configurationinteraction calculations. The calculated probabilities for (V)0, j)0-5) are shown to display resonance structures, a feature also visible to some extent in the calculated total cross sections for (V)0, j)0). A comparison between the calculated centrifugal-sudden and coupled-channel reaction probabilities validate the former approximation for the title system. Rate constants calculated using a uniform J-shifting scheme and averaged over a Boltzmann distribution of rotational states are shown to be in good agreement with the available experimental values. Comparisons with other theoretical results are also made.
Chemical Physics, 1997
This paper presents reactive state-to-state J=0 probabilities for the title system as obtained in a four-mathematical-dimensional quantum mechanical treatment. The present treatment differs from our previous one by the fact that in addition to the three Jacobi radial coordinates also the angular coordinate related to the H2 axis is treated as coordinates. As a result only the Jacobi angle related to the OH axis is treated as a parameter and the final probabilities follow from an integration over this angle (the out-of-plane angle, β, is eliminated by using a β-averaged potential). The calculations yielded final rotational and vibrational distributions that were analyzed and discussed with respect to more accurate (i.e., five- and six-mathematical-dimensional) results.
The Journal of Chemical Physics, 2012
We present wave packet calculations of total and state-to-state reaction probabilities and integral cross sections for the nonadiabatic dynamics of the O( 3 P)+HF → F( 2 P)+OH( 2 ) reaction at hyperthermal collision energies ranging from 1.2 to 2.4 eV. The validity of the centrifugal sudden approximation is discussed for the title reaction and a comprehensive investigation of the influence of nonadiabatic effects on the dynamics of this reactive system at high (hyperthermal) collision energies is presented. In general, nonadiabatic effects are negligible for averaged observables, such as total reaction probabilities and integral cross sections, but they are clearly observed in detailed observables such as rotationally state-resolved reaction probabilities. A critical discussion of nonadiabatic effects on the dynamics of the title reaction is carried out by comparing with the reverse reaction and the characteristics of the adiabatic and diabatic potential energy surfaces involved.
The Journal of Chemical Physics, 2000
We report results of quantum wave packet calculations of the O( 1 D)ϩHCl(vϭ0,j)→ClOϩH, OHϩCl, reactions for zero and nonzero total angular momentum, J, ͑using the centrifugal sudden approximation͒, and using a new fit to extensive ab initio calculations of a global potential ͓K. A. Peterson, S. Skokov, and J. M. Bowman, J. Chem. Phys. 111, 2445 ͑1999͔͒. Initial state-selected and cumulative reaction probabilities to form each set of products for Jϭ0 are calculated by a direct summation of the initial state-selected reaction probabilities. We propose and test a simple energy-shifting approximation that relates the initial state-selected reaction probability for arbitrary j to the one for jϭ0. Extensions of standard J-and K-shifting methods are suggested and applied to both reaction channels. In doing this extension the adiabatic rotation approximation is used to determine the rotational barriers in the entrance and exit channels. The energy dependence of the reaction cross sections to form the two products is calculated for O( 1 D)ϩHCl(vϭ0,jϭ0) using Jand K-shifting and compared at two translational energies to results of quasiclassical trajectory calculations. The thermal rate constants for the two reaction channels are calculated from 200 to 400 K and compared to experiment.