Quantum dynamics study of the K+HF(v=–2,j=)→KF+H reaction and comparison with quasiclassical trajectory results

Abstract

Extensive quantum real wave packet calculations within the helicity decoupling approximation are used to analyze the influence of the HF vibrational excitation on the K+HF(v=0-2,j=0)-->KF+H reaction. Quantum reaction probabilities P and reaction cross sections sigma are compared with corresponding quasiclassical trajectory (QCT) results. Disregarding threshold regions for v=0 and 1 (v=2 has no threshold), both approaches lead to remarkably similar results, particularly for sigma, validating the use of the QCT method for this system. When moving from v=0 to v=1 there is a large increase in P and sigma, as expected for a late barrier system. For v=2 the reaction becomes exoergic and P approximately 0.95 (with the exception of large total angular momenta where centrifugal barriers play a role). While substantial vibrational enhancement of the reactivity is thus seen, it is still quite less than that inferred from experimental data in the intermediate and high collision energy ranges. The origin of this discrepancy is unclear.

Control of Mode/Bond Selectivity and Product Energy Disposal by the Transition State: X + H2O (X = H, F, O(3P), and Cl) Reactions

“…Due to the hydrogen abstraction nature of these reactions, a full-dimensional quantum treatment of the dynamics is essential to describe quantum effects such as tunneling, zero-point energy, and resonances. The mode selectivity in the late barrier H + H 2 O system has been investigated with both classical − and quantum models. − Very recently, an extensive investigation of mode selectivity in this reaction was reported by Fu and Zhang on an accurate global PES . Their calculated energy dependence of the integral cross sections (ICSs), which is reproduced in Figure , will be used in our analysis.…”

Time-Dependent Quantum Dynamics Study of the Ne + H2+ (v = 0−9) and D2+ (v = 0−12) Proton Transfer Reactions at Thermal Collision Energies

“…We calculated quantum reaction probabilities ( P ) via the RWP method of Gray and Balint-Kurti, defining an initial wave packet at a total angular momentum quantum number ( J ) in reactant Jacobi coordinates ( R , r , and γ) and propagating only the real part of it on the best analytical ground PES of the NeH 2 + system available (PHHJ-3 surface) by using the CS approximation . The RWP method in the context of different approximations (CS and J -shifting methods) has been successfully applied to a variety of triatomic and tetratomic reactions (see, e.g., refs and − ).…”

Higher-order split operator schemes for solving the Schrödinger equation in the time-dependent wave packet method: applications to triatomic reactive scattering calculations

“…92 In a CRWP calculation, only real arithmetic is carried out which not only improves the numerical efficiency but also reduces memory requirements, compared with the TC polynomial expansion method. 93 Since its introduction, it has been applied to study many reactive scattering processes at the level of calculating total reactive probabilities by the flux formalism or at the state-to-state level but with the restriction of J = 0 using Jacobi coordinate, including H + O 2 , 27,42,43,[94][95][96][97][98][99] Br + H 2 , 100 C + H 2 /D 2 /HD, [101][102][103] Cl + H 2 , 104,105 F + H 2 , 27,106 F + OH, 106 F + HCl, 107 K + HF, 108 Li + HF 106,109 N + O 2 , [110][111][112] O + HD/H 2 , 99,[113][114][115][116][117][118] O + HCl, [119][120][121][122][123][124][125] O + CN, 126 O + OH, 127,128 O + O 2 , 27 S + D 2 /HD, …”