Accurate quantum wave packet calculations for the F + HCl → Cl + HF reaction on the ground 12<i>A</i>′ potential energy surface

Bulut, Niyazi; Kłos, Jacek; Alexander, Millard H.

doi:10.1063/1.3692328

Cited by 16 publications

(31 citation statements)

References 20 publications

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“…The energetic barrier on this PES is 3.8 kcal mol À1 . The work of Bulut et al 29 shows that the rate constants predicted by calculations with this PES are an order of magnitude smaller than experimental estimates. 16,17 In addition, they concluded that quantum tunneling will not make a significant contribution to the thermal reaction rates.…”

Section: Discussionmentioning

confidence: 97%

“…We note that the helicity limit of K max = min( J,40) is much larger than the value of 7 used in a recent quantum wave-packet calculation of the total F + HCl reaction cross-sections. 29 Determination of the latter does not require propagation of the wavepacket as far into the product arrangement as is necessary for the determination of final-state resolved crosssections. An accurate description of the wavepacket in the product arrangement in terms of reactant-arrangement rotational functions requires a larger helicity basis.…”

Section: Iiia Details Of Scattering Calculationsmentioning

confidence: 99%

“…25 The transition state on this PES is located at a strongly bent geometry (+FHCl = 123.51) with a classical barrier height of 3.8 kcal mol À1 relative to F + HCl reactants. An interesting feature of this reaction is that the reactant rotational excitation leads to a significant enhancement in reactivity, [26][27][28][29] …”

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confidence: 99%

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State-to-state quantum dynamics of the F + HCl (vi = 0, ji = 0) → HF(vf, jf) + Cl reaction on the ground state potential energy surface

Guo

Kłos

et al. 2013

Phys. Chem. Chem. Phys.

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The state-to-state reaction dynamics of the title reaction is investigated on the ground electronic state potential energy surface using two quantum dynamical methods. The results obtained using the Chebyshev real wave packet method are in excellent agreement with those obtained using the time-independent method, except at low translational energies. It is shown that this exothermic hydrogen abstraction reaction is direct, resulting in a strong back-scattered bias in the product angular distribution. The HF product is highly excited internally. Agreement with available experimental data is only qualitative. We discuss several possible causes of disagreement with experiment.

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Section: Discussionmentioning

confidence: 97%

Section: Iiia Details Of Scattering Calculationsmentioning

confidence: 99%

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State-to-state quantum dynamics of the F + HCl (vi = 0, ji = 0) → HF(vf, jf) + Cl reaction on the ground state potential energy surface

Guo

Kłos

et al. 2013

Phys. Chem. Chem. Phys.

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“…[26][27][28] On the a) Authors to whom correspondence should be addressed. Electronic addresses: fengyanwang@fudan.edu.cn; czako@chem.elte.hu; yangmh@ wipm.ac.cn; kliu@pub.iams.sinica.edu.tw; and hguo@unm.edu other hand, there were many theoretical studies of the rotational effect, [29][30][31][32][33][34][35][36][37][38][39][40] although few were concerned with rotation of polyatomic reactants. [41][42][43][44][45] Since the energy gap between rotational states is typically much smaller than that for vibration, the impact of rotational excitation is often greater per unit energy than its vibrational counterpart.…”

Section: Introductionmentioning

confidence: 99%

Rotational mode specificity in the Cl + CHD3 → HCl + CD3 reaction

Wang

Jiang

et al. 2014

The Journal of Chemical Physics

109

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By exciting the rotational modes of vibrationally excited CHD3(v1 = 1, JK), the reactivity for the Cl + CHD3 → HCl + CD3 reaction is observed enhanced by as much as a factor of two relative to the rotationless reactant. To understand the mode specificity, the reaction dynamics was studied using both a reduced-dimensional quantum dynamical model and the conventional quasi-classical trajectory method, both of which reproduced qualitatively the measured enhancements. The mechanism of enhancement was analyzed using a Franck-Condon model and by inspecting trajectories. It is shown that the higher reactivity for higher J states of CHD3 with K = 0 can be attributed to the enlargement of the cone of acceptance. On the other hand, the less pronounced enhancement for the higher J = K states is apparently due to the fact that the rotation along the C-H bond is less effective in opening up the cone of acceptance.

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“…Indeed, several recent quantum dynamics studies have been devoted to the exploration of rotational effects in bimolecular reactions. 6,[9][10][11][12][13][14][15][16][17][18][19][20][21][22] In this work, we focus on the rotational mode specificity in a prototypical penta-atom reactive system, namely, the H 2 + NH 2 → H + NH 3 reaction. This reaction has been the subject of extensive theoretical investigations.…”

Section: Introductionmentioning

confidence: 99%

Effects of reactant rotational excitations on H2 + NH2 → H + NH3 reactivity

Song

Guo

2014

The Journal of Chemical Physics

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Rotational mode specificity of the title reaction is examined using an initial state selected time-dependent wave packet method on an accurate ab initio based global potential energy surface. This penta-atomic reaction presents an ideal system to test several dynamical approximations, which might be useful for future quantum dynamics studies of polyatomic reactions, particularly with rotationally excited reactants. The first approximation involves a seven-dimensional (7D) model in which the two non-reactive N-H bonds are fixed at their equilibrium geometry. The second is the centrifugal sudden (CS) approximation within the 7D model. Finally, the J-shifting (JS) model is tested, again with the fixed N-H bonds. The spectator-bond approximation works very well in the energy range studied, while the centrifugal sudden and J-shifting integral cross sections (ICSs) agree satisfactorily with the coupled-channel counterparts in the low collision energy range, but deviate at the high energies. The calculated integral cross sections indicate that the rotational excitation of H2 somewhat inhibits the reaction while the rotational excitations of NH2 have little effect. These findings are compared with the predictions of the sudden vector projection model. Finally, a simple model is proposed to predict rotational mode specificity using K-averaged reaction probabilities.

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Accurate quantum wave packet calculations for the F + HCl → Cl + HF reaction on the ground 12A′ potential energy surface

Abstract: We present converged exact quantum wave packet calculations of reaction probabilities, integral cross sections, and thermal rate coefficients for the title reaction.

Cited by 16 publications

References 20 publications

State-to-state quantum dynamics of the F + HCl (vi = 0, ji = 0) → HF(vf, jf) + Cl reaction on the ground state potential energy surface

State-to-state quantum dynamics of the F + HCl (vi = 0, ji = 0) → HF(vf, jf) + Cl reaction on the ground state potential energy surface

Rotational mode specificity in the Cl + CHD3 → HCl + CD3 reaction

Effects of reactant rotational excitations on H2 + NH2 → H + NH3 reactivity

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