Observation of a transition state resonance in the integral cross section of the F+HD reaction

Skodje, Rex T.; Skouteris, Dimitrios; Manolopoulos, David E.; Lee, Shih‐Huang; Dong, Feng; Liu, Kopin

doi:10.1063/1.481041

Cited by 189 publications

(226 citation statements)

References 76 publications

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“…It is well understood that impact parameter averaging effectively smears the resonance over a large energy range, making it very challenging to identify in reactive cross sections. 32 In fact, it was only very recently 33,34 that a clear resonance signature was observed in any bimolecular reaction, i.e., FϩHD→DϩHF, and for that case it was clearly observed only because it was narrow, isolated, and occurred below the threshold for direct reaction. The HϩH 2 resonances are much more difficult to observe since they lie at fairly high energies and, according to theoretical estimates, [35][36][37] are extremely short lived, Ͻ20 fs.…”

Section: Introductionmentioning

confidence: 99%

A fully state- and angle-resolved study of the H+HD→D+H2 reaction: Comparison of a molecular beam experiment to ab initio quantum reaction dynamics

Chao

Harich

Dai

et al. 2002

The Journal of Chemical Physics

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We present the results of a joint experimental and theoretical investigation of the reaction dynamics of the HϩHD→DϩH 2 chemical reaction. The experiment was performed using a crossed molecular beam apparatus that employed the Rydberg-atom time-of-flight detection scheme for the product D atom. The photolysis of a HI precursor molecule produced a beam source of hot H atoms, which, when crossed with a cold HD beam, yielded two well-defined center-of-mass collision energies, E C ϭ0.498 and 1.200 eV. The resolution of the experiment was sufficient to allow the measurement of the rovibrationally state-resolved differential cross section from the ground state of the HD reagent. The reaction was modeled theoretically using a converged coupled channel scattering calculation employing the BKMP2 potential energy surface: The S matrix was computed on a grid of 56 energies in the range E C ϭ0.245-1.551 eV. It is found that the experimental and theoretical state-to-state differential cross sections are in quantitative agreement at the two experimental energies. The geometric phase, which was not included in the calculation, is apparently not required at the energies considered. The spin statistics for the two identical protons is observed to have a dramatic effect on the rotational distribution of H 2 products, giving rise to a saw-toothed distribution with odd-jЈϾeven-jЈ. The differential cross section for several of the product states exhibited a dramatic forward peak that may be the signature of trapped quantum states near the saddle point. A detailed analysis of the reaction attributes is presented based on the energy dependence of the computed S matrix.

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Section: Introductionmentioning

confidence: 99%

A fully state- and angle-resolved study of the H+HD→D+H2 reaction: Comparison of a molecular beam experiment to ab initio quantum reaction dynamics

Chao

Harich

Dai

et al. 2002

The Journal of Chemical Physics

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“…1(a), the transition state resonance region, Σ T SR , can be defined as the region enclosing the "elbow" of the PES; the reactants region, Σ R , as the region enclosing only the entrance F+HD channel; and the products region, Σ P , as the region above Σ T SR (which would include both exit channels). It is worth mentioning that this approach differs from the spectral quantization analysis performed by Skodje et al [32]. In that work, the transition state was probed by explicitly setting the initial WP at this region.…”

Section: Analysis Of Wp Dynamics and Survival Probabilitiesmentioning

confidence: 99%

“…In this sense, the F+HD reaction constitutes a paradigmatic system. This system has been actively investigated in the last decade due to the the observation through molecular beam experiments of a resonance for the reactive channel F+HD → HF+D [32,33]. In the differential cross section, this dynamical feature manifests as a sharp variation of the peaks along the forward-backward scattering directions and, in the corresponding integral cross section, as a step-like profile.…”

Section: Introductionmentioning

confidence: 99%

“…Although the maximum peak associated with the resonance was not reproduced in those studies, the rotational motion was found to play a significant role in the overall reaction mechanism. Thus, in order to provide a correct description of the dynamics of the F+HD → FH+D reaction, a complete threedimensional (3D) QM approach is required [32].…”

Section: Introductionmentioning

confidence: 99%

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Investigating transition state resonances in the time domain by means of Bohmian mechanics: The F+HD reaction

Sanz¹,

López‐Durán²,

González‐Lezana³

2012

Chemical Physics

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In this work, we investigate the existence of transition state resonances on atom-diatom reactive collisions from a timedependent perspective, stressing the role of quantum trajectories as a tool to analyze this phenomenon. As it is shown, when one focusses on the quantum probability current density, new dynamical information about the reactive process can be extracted. In order to detect the effects of the different rotational populations and their dynamics/coherences, we have considered a reduced two-dimensional dynamics obtained from the evolution of a full three-dimensional quantum time-dependent wave packet associated with a particular angle. This reduction procedure provides us with information about the entanglement between the radial degrees of freedom (r, R) and the angular one (γ), which can be considered as describing an environment. The combined approach here proposed has been applied to study the F+HD reaction, for which the FH+D product channel exhibits a resonance-mediated dynamics.

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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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Observation of a transition state resonance in the integral cross section of the F+HD reaction

Abstract: State-to-state reactive differential cross sections for the H + H 2 → H 2 + H reaction on five different potential energy surfaces employing a new quantum wavepacket computer code: DIFFREALWAVE

Cited by 189 publications

References 76 publications

A fully state- and angle-resolved study of the H+HD→D+H2 reaction: Comparison of a molecular beam experiment to ab initio quantum reaction dynamics

A fully state- and angle-resolved study of the H+HD→D+H2 reaction: Comparison of a molecular beam experiment to ab initio quantum reaction dynamics

Investigating transition state resonances in the time domain by means of Bohmian mechanics: The F+HD reaction

Chemistry at surfaces: from ab initio structures to quantum dynamics

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