Transition state in metal atom reactions

Mestdagh, J. M.; Soep, B.; Gaveau, M.‐A.; Visticot, J. P.

doi:10.1080/0144235031000086391

Cited by 47 publications

(25 citation statements)

References 274 publications

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“…107 The ground electronic state is the result of a curve crossing between a covalent and an ionic electronic state correlating with reactants and products, respectively. The saddle point in the ground electronic state is the result of the crossing.…”

Section: A H + D 2 Collision In Reactantmentioning

confidence: 99%

Differential Cross Sections and Product Rotational Polarization in A + BC Reactions Using Wave Packet Methods: H⁺ + D₂ and Li + HF Examples

et al. 2009

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The state-to-state differential cross sections for some atom + diatom reactions have been calculated using a new wave packet code, MAD-WAVE3, which is described in some detail and uses either reactant or product Jacobi coordinates along the propagation. In order to show the accuracy and efficiency of the coordinate transformation required when using reactant Jacobi coordinates, as recently proposed [ J. Chem. Phys. 2006 , 125 , 054102 ], the method is first applied to the H + D(2) reaction as a benchmark, for which exact time-independent calculations are also performed. It is found that the use of reactant coordinates yields accurate results, with a computational effort slightly lower than that when using product coordinates. The H(+) + D(2) reaction, with the same masses but a much deeper insertion well, is also studied and exhibits a completely different mechanism, a complex-forming one which can be treated by statistical methods. Due to the longer range of the potential, product Jacobi coordinates are more efficient in this case. Differential cross sections for individual final rotational states of the products are obtained based on exact dynamical calculations for some selected total angular momenta, combined with the random phase approximation to save the high computational time required to calculate all partial waves with very long propagations. The results obtained are in excellent agreement with available exact time-independent calculations. Finally, the method is applied to the Li + HF system for which reactant coordinates are very well suited, and quantum differential cross sections are not available. The results are compared with recent quasiclassical simulations and experimental results [J. Chem. Phys. 2005, 122, 244304]. Furthermore, the polarization of the product angular momenta is also analyzed as a function of the scattering angle.

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Section: A H + D 2 Collision In Reactantmentioning

confidence: 99%

Differential Cross Sections and Product Rotational Polarization in A + BC Reactions Using Wave Packet Methods: H⁺ + D₂ and Li + HF Examples

et al. 2009

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“…Once the barrier is overcome, the HF − complex quickly dissociates producing fast H-fragments which fly away and leave the Li + F − products in a strongly attractive quantum state. This so-called direct interaction with product repulsion (DIPR) mechanism has recently been reviewed by Mestdagh et al 61 The mechanism is typical for metal atom (M) -hydrogen halide (HX) reactions: the electron jumps from M forming HX − transient, which is unstable and dissociates rapidly leaving the M + X − ionic products. Within this mechanism the product distribution is formed by the transition state region under the condition of fast dissociation.…”

Section: LI + Hf Chemical Reactionmentioning

confidence: 99%

Polarization of molecular angular momentum in the chemical reactions Li + HF and F + HD

Krasilnikov

Popov

Roncero

et al. 2013

The Journal of Chemical Physics

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The quantum mechanical approach to vector correlation of angular momentum orientation and alignment in chemical reactions [G. Balint- (2011)] reactions for which accurate scattering information has become recently available through time-dependent and time-independent approaches. Application of the theory to two important particular cases of the reactive collisions has been considered: (i) the influence of the angular momentum polarization of reactants in the entrance channel on the spatial distribution of the products in the exit channel and (ii) angular momentum polarization of the products of the reaction between unpolarized reactants. In the former case, the role of the angular momentum alignment of the reactants is shown to be large, particularly when the angular momentum is perpendicular to the reaction scattering plane. In the latter case, the orientation and alignment of the product angular momentum was found to be significant and strongly dependent on the scattering angle. The calculation also reveals significant differences between the vector correlation properties of the two reactions under study which are due to difference in the reaction mechanisms. In the case of F + HD reaction, the branching ratio between HF and DF production points out interest in the insight gained into the detailed dynamics, when information is available either from exact quantum mechanical calculations or from especially designed experiments. Also, the geometrical arrangement for the experimental determination of the product angular momentum orientation and alignment based on a compact and convenient spherical tensor expression for the intensity of the resonance enhanced multiphoton ionization (REMPI 2 + 1) signal is suggested. © 2013 AIP Publishing LLC.

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“…Because matrix studies offer limited flexibility to investigate the effect of the thickness of the solvation layer, studies on doped clusters in the gas phase have been undertaken using different spectroscopic techniques. 8 Fluorescence spectroscopy is often used to identify the products of photochemical reactions in clusters, [9][10][11][12][13][14][15][16][17][18][19] and femtosecond laser excitation provides information on the time evolution of reactions. 20,21 Femtosecond photoelectron spectroscopy on mass selective iodine Ar anion clusters showed that a solvation shell of 20 Ar atoms was sufficient to induce recombination of the iodine fragments 21,20 and similar experiments on iodine in neutral Ar clusters revealed that caging was completed within 10 −12 s. [22][23][24] A thorough investigation of the cage effect of hydrogen halides doped into the interior or onto the surface of clusters and aligned in a static electric and a laser field was recently undertaken by Buck and co-workers.…”

Section: Introductionmentioning

confidence: 99%

Photochemical processes in doped argon-neon core-shell clusters: The effect of cage size on the dissociation of molecular oxygen

Laarmann

Wabnitz

Haeften

et al. 2008

The Journal of Chemical Physics

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The caging effect of the host environment on photochemical reactions of molecular oxygen is investigated using monochromatic synchrotron radiation and spectrally resolved fluorescence. Oxygen doped clusters are formed by coexpansion of argon and oxygen, by pickup of molecular oxygen or by multiple pickup of argon and oxygen by neon clusters. Sequential pickup provides radially ordered core-shell structures in which a central oxygen molecule is surrounded by argon layers of variable thickness inside large neon clusters. Pure argon and core-shell argon-neon clusters excited with ϳ12 eV monochromatic synchrotron radiation show strong fluorescence in the vacuum ultraviolet ͑vuv͒ spectral range. When the clusters are doped with O 2 , fluorescence in the visible ͑vis͒ spectral range is observed and the vuv radiation is found to be quenched. Energy-resolved vis fluorescence spectra show the 2 1 ⌺ + → 1 1 ⌺ + ͑ArO͑ 1 S͒ → ArO͑ 1 D͒͒ transition from argon oxide as well as the vibrational progression A Ј 3 ⌬ u ͑ Ј=0͒ → X 3 ⌺ g − ͑ Љ͒ of O 2 indicating that molecular oxygen dissociates and occasionally recombines depending on the experimental conditions. Both the emission from ArO and O 2 as well the vuv quenching by oxygen are found to depend on the excitation energy, providing evidence that the energy transfer from the photoexcited cluster to the embedded oxygen proceeds via the O 2 + ground state. The O 2 + decays via dissociative recombination and either reacts with Ar resulting in electronically excited ArO or it recombines to O 2 within the Ar cage. Variation of the Ar layer thickness in O 2 -Ar-Ne core-shell clusters shows that a stable cage is formed by two solvation layers.

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Transition state in metal atom reactions

Cited by 47 publications

References 274 publications

Differential Cross Sections and Product Rotational Polarization in A + BC Reactions Using Wave Packet Methods: H⁺ + D₂ and Li + HF Examples

Differential Cross Sections and Product Rotational Polarization in A + BC Reactions Using Wave Packet Methods: H⁺ + D₂ and Li + HF Examples

Polarization of molecular angular momentum in the chemical reactions Li + HF and F + HD

Photochemical processes in doped argon-neon core-shell clusters: The effect of cage size on the dissociation of molecular oxygen

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Transition state in metal atom reactions

Cited by 47 publications

References 274 publications

Differential Cross Sections and Product Rotational Polarization in A + BC Reactions Using Wave Packet Methods: H+ + D2 and Li + HF Examples

Differential Cross Sections and Product Rotational Polarization in A + BC Reactions Using Wave Packet Methods: H+ + D2 and Li + HF Examples

Polarization of molecular angular momentum in the chemical reactions Li + HF and F + HD

Photochemical processes in doped argon-neon core-shell clusters: The effect of cage size on the dissociation of molecular oxygen

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Product

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Differential Cross Sections and Product Rotational Polarization in A + BC Reactions Using Wave Packet Methods: H⁺ + D₂ and Li + HF Examples

Differential Cross Sections and Product Rotational Polarization in A + BC Reactions Using Wave Packet Methods: H⁺ + D₂ and Li + HF Examples