A hierarchical construction scheme for accurate potential energy surface generation: An application to the F+H2 reaction

Fu, Bina; Xu, Xin; Zhang, Dong H.

doi:10.1063/1.2955729

Cited by 72 publications

(107 citation statements)

References 28 publications

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“…148 Note that Ref. 23 found the position and residue of the leading Regge pole using Thiele rational interpolation, 140,141 but no Watson/Regge calculations of the DCS were carried out.…”

Section: J Discussion Of the F + H 2 Resultsmentioning

confidence: 99%

Resonance Regge poles and the state-to-state F + H2 reaction: QP decomposition, parametrized S matrix, and semiclassical complex angular momentum analysis of the angular scattering

Connor

2013

The Journal of Chemical Physics

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Three new contributions to the complex angular momentum (CAM) theory of differential cross sections (DCSs) for chemical reactions are reported. They exploit recent advances in the Padé reconstruction of a scattering (S) matrix in a region surrounding the ReJ axis, where J is the total angular momentum quantum variable, starting from the discrete values, J = 0, 1, 2, .... In particular, use is made of Padé continuations obtained by Sokolovski, Castillo, and Tully [Chem. Phys. Lett. 313, 225 (1999)] for the S matrix of the benchmark F + H2(v(i) = 0, j(i) = 0, m(i) = 0) → FH(v(f) = 3, j(f) = 3, m(f) = 0) + H reaction. Here v(i), j(i), m(i) and v(f), j(f), m(f) are the initial and final vibrational, rotational, and helicity quantum numbers, respectively. The three contributions are: (1) A new exact decomposition of the partial wave (PW) S matrix is introduced, which is called the QP decomposition. The P part contains information on the Regge poles. The Q part is then constructed exactly by subtracting a rapidly oscillating phase and the PW P matrix from the input PW S matrix. After a simple modification, it is found that the corresponding scattering subamplitudes provide insight into the angular-scattering dynamics using simple partial wave series (PWS) computations. It is shown that the leading n = 0 Regge pole contributes to the small-angle scattering in the centre-of-mass frame. (2) The Q matrix part of the QP decomposition has simpler properties than the input S matrix. This fact is exploited to deduce a parametrized (analytic) formula for the PW S matrix in which all terms have a direct physical interpretation. This is a long sort-after goal in reaction dynamics, and in particular for the state-to-state F + H2 reaction. (3) The first definitive test is reported for the accuracy of a uniform semiclassical (asymptotic) CAM theory for a DCS based on the Watson transformation. The parametrized S matrix obtained in contribution (2) is used in both the PW and semiclassical parts of the calculation. Powerful uniform asymptotic approximations are employed for the background integral; they allow for the proximity of a Regge pole and a saddle point. The CAM DCS agrees well with the PWS DCS, across the whole angular range, except close to the forward and backward directions, where, as expected, the CAM theory becomes non-uniform. At small angles, θ(R) ≲ 40°, the PWS DCS can be reproduced using a nearside semiclassical subamplitude, which allows for a pole being close to a saddle point, plus the farside surface wave of the n = 0 pole sub-subamplitude, with the oscillations in the DCS arising from nearside-farside interference. This proves that the n = 0 Regge resonance pole contributes to the small-angle scattering.

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“…148 Note that Ref. 23 found the position and residue of the leading Regge pole using Thiele rational interpolation, 140,141 but no Watson/Regge calculations of the DCS were carried out.…”

Section: J Discussion Of the F + H 2 Resultsmentioning

confidence: 99%

Resonance Regge poles and the state-to-state F + H2 reaction: QP decomposition, parametrized S matrix, and semiclassical complex angular momentum analysis of the angular scattering

Connor

2013

The Journal of Chemical Physics

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“…10a. 63 This recent ab initio PES is known to accurately reproduce many resonance features experimentally observed for the F + HD reaction. [49][50][51][52] Positions and widths of the metastable states affecting the state-to-sate integral cross sections, obtained by the Padé reconstruction of the S-matrix element in the complex energy plane, are shown in Fig.…”

Section: The Near-threshold Range: Resonances B C D and Ementioning

confidence: 99%

Complex angular momentum theory of state-to-state integral cross sections: resonance effects in the F + HD → HF(v′ = 3) + D reaction

Sokolovski

Akhmatskaya

Echeverría‐Arrondo

et al. 2015

Phys. Chem. Chem. Phys.

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State-to-state reactive integral cross sections (ICSs) are often affected by quantum mechanical resonances, especially near a reactive threshold. An ICS is usually obtained by summing partial waves at a given value of energy. For this reason, the knowledge of pole positions and residues in the complex energy plane is not sufficient for a quantitative description of the patterns produced by resonance. Such description is available in terms of the poles of an S-matrix element in the complex plane of the total angular momentum. The approach was recently implemented in a computer code ICS_Regge, available in the public domain [Comput. Phys. Commun., 2014, 185, 2127. In this paper, we employ the ICS_Regge package to analyse in detail, for the first time, the resonance patterns predicted for integral cross sections

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“…75 In Ref. 76, close coupling quantum integral cross sections and rate constants for both reactive channels calculated with a new ab initio PES recently published 77 by Fu, Xu, and Zhang (FXZ) were compared with several sets of experimental data. The vibrationally selected integral cross sections for the HF channel were shown for the first time in excellent agreement with experiments, 78 notably for the HF(v = 3) channel, where the presence of a broad maximum has revealed the role of a new direct mechanism acting selectively on the FXZ PES.…”

Section: F + Hd 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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A hierarchical construction scheme for accurate potential energy surface generation: An application to the F+H2 reaction

Cited by 72 publications

References 28 publications

Resonance Regge poles and the state-to-state F + H2 reaction: QP decomposition, parametrized S matrix, and semiclassical complex angular momentum analysis of the angular scattering

Resonance Regge poles and the state-to-state F + H2 reaction: QP decomposition, parametrized S matrix, and semiclassical complex angular momentum analysis of the angular scattering

Complex angular momentum theory of state-to-state integral cross sections: resonance effects in the F + HD → HF(v′ = 3) + D reaction

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

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