Reactive Resonance in a Polyatomic Reaction

Shiu, Weicheng; Lin, Jim J.; Liu, Kopin

doi:10.1103/physrevlett.92.103201

Cited by 140 publications

(154 citation statements)

References 19 publications

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“…Within the last decade, significant progress towards the investigation of polyatomic reactions has been made and experiments studying state-to-state reactive scattering of six atom reactions as F + CH 4 → HF + CH 3 (Refs. [1][2][3] or Cl + CH 4 → HCl + CH 3 (Refs. 4-7) have been published.…”

Section: Introductionmentioning

confidence: 99%

State-to-state reaction probabilities within the quantum transition state framework

Welsch

Huarte-Larrañaga

Manthe

2012

The Journal of Chemical Physics

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Rigorous quantum dynamics calculations of reaction rates and initial state-selected reaction probabilities of polyatomic reactions can be efficiently performed within the quantum transition state concept employing flux correlation functions and wave packet propagation utilizing the multi-configurational time-dependent Hartree approach. Here, analytical formulas and a numerical scheme extending this approach to the calculation of state-to-state reaction probabilities are presented. The formulas derived facilitate the use of three different dividing surfaces: two dividing surfaces located in the product and reactant asymptotic region facilitate full state resolution while a third dividing surface placed in the transition state region can be used to define an additional flux operator. The eigenstates of the corresponding thermal flux operator then correspond to vibrational states of the activated complex. Transforming these states to reactant and product coordinates and propagating them into the respective asymptotic region, the full scattering matrix can be obtained. To illustrate the new approach, test calculations study the D + H 2 (ν, j ) → HD(ν , j ) + H reaction for J = 0.

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Section: Introductionmentioning

confidence: 99%

State-to-state reaction probabilities within the quantum transition state framework

Welsch

Huarte-Larrañaga

Manthe

2012

The Journal of Chemical Physics

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“…A tunable infrared (IR) OPO/A (optical parametric oscillator/amplifier) was tuned to the 3 1 0 R(1) transition to excite a fraction of the CH 4 molecules to a single rovibrational state (v 3 = 1, j = 2) through a multipass ring reflector. 25 After the collisions, the ground state CH 3 (0 0 ) products were detected by a (2+1) resonance-enhanced multiphoton ionization (REMPI) method 26,27 and recorded by a time-sliced, velocity-imaging technique. 28 Due to the low S/N ratios, the probe laser wavelength was fixed at the peak of the Q-head; thus, mainly the low N-states of CH 3 (0 0 ) were sampled.…”

mentioning

confidence: 99%

Communication: Imaging the effects of the antisymmetric-stretching excitation in the O(3P) + CH4(v3 = 1) reaction

Pan

Liu

2014

The Journal of Chemical Physics

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Effects of one-quantum excitation of the antisymmetric-stretching mode of CH4(v3 = 1) on the O(3P) + CH4 reaction were studied in a crossed-beam, ion-imaging experiment. In the post-threshold region, we found that (1) the product state distributions are dominated by the CH3(00) + OH(v′ = 1) pair, (2) the product angular distributions extend toward sideways from the backward dominance of the ground-state reaction, and (3) vibrational excitation exerts a positive effect on reactivity, but translational energy is more efficient in promoting the rate of this central-barrier reaction. All major findings agree reasonably well with recent theoretical results. Some remaining questions are pointed out.

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“…The H + H 2 isotopic family of reactions is the best known example for quantized dynamical bottlenecks which lead to an observable time-delayed mechanism [147,148], and interference features [149,150]. The F + HD→HF + D reaction is the first reaction for which conclusive evidence has been found for a Feshbach resonance in a full collisional dynamics [151,152] and only recently experimental evidence has been found for some polyatomic reactions [153][154][155]. We found clear quantum signatures in global observables like total EleyRideal cross sections, which indicate that some cautions are needed when applying classical methods to light atom dynamics, even when the reaction system, the reaction conditions or the observable to be computed suggest them to be adequate.…”

Section: Quantum Effects In Eley-rideal Hydrogen Formation From Chemimentioning

confidence: 99%

Chemistry at surfaces: from ab initio structures to quantum dynamics

et al. 2007

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Recent years have witnessed an ever growing interest in theoretically studying chemical processes at surfaces. Apart from the interest in catalysis, electrochemistry, hydrogen economy, green chemistry, atmospheric and interstellar chemistry, theoretical understanding of the molecule-surface chemical bonding and of the microscopic dynamics of adsorption and reaction of adsorbates are of fundamental importance for modeling known processes, understanding new experimental data, predicting new phenomena, controlling reaction pathways. In this work, we review the efforts we have made in the last few years in this exciting field. We first consider the energetics and the structural properties of some adsorbates on metal surfaces, as deduced by converged, first-principles, plane-wave calculations within the slab-supercell approach. These studies comprise water adsorption on Ru(0001), a subject of very intense debate in the past few years, and oxygen adsorption on aluminum, the prototypical example of metal passivation. Next, we address dynamical processes at surfaces with classical and quantum methods. Here the main interest is in hydrogen dynamics on metallic and semi-metallic surfaces, because of its importance for hydrogen storage and interstellar chem- istry. Hydrogen sticking is studied with classical and quasi-classical means, with particular emphasis on the relaxation of hot-atoms following dissociative chemisorption. Hot atoms dynamics on metal surfaces is investigated in the reverse, hydrogen recombination process and compared to Eley-Rideal dynamics. Finally, Eley-Rideal, collision-induced desorption, and adsorbate-induced trapping are studied quantum mechanically on a graphite surface, and unexpected quantum effects are observed.

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Reactive Resonance in a Polyatomic Reaction

Cited by 140 publications

References 19 publications

State-to-state reaction probabilities within the quantum transition state framework

State-to-state reaction probabilities within the quantum transition state framework

Communication: Imaging the effects of the antisymmetric-stretching excitation in the O(3P) + CH4(v3 = 1) reaction

Chemistry at surfaces: from ab initio structures to quantum dynamics

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