Reactive excitation functions for F+p-H2/n-H2/D2 and the vibrational branching for F+HD

Abstract

Complementary to our recent report on the F+HD reaction, the reactive excitation functions for the other isotopomers are presented. Through analysis of the differential cross section data, the collisional energy dependencies of product vibrational branchings for F+HD are also reported here. Several important conclusions can be drawn from this work. First, the transition-state properties, in particular the barrier height, of this reaction are well-characterized by the SW PES, despite its neglect of spin–orbit couplings. Second, contrary to the theoretical conclusion in recent literatures, an experimental observation is presented which seems to suggest that a resonance may indeed exist for the F+H2 reaction in support of the original interpretation proposed by Lee and co-workers. Third, the vibrational branching for the F+HD→HF+D reaction elucidates another facet of resonance effects in the integral cross sections. Finally, the nonadiabatic reactivity of the spin–orbit excited F*(2P1/2) atom is found to be small, which is in line with the conclusion inferred from a most recent, full quantum mechanical multisurface calculation.

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

“…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. The state-to-state ICS presented in Fig.…”

Benchmark Quantum Mechanical Calculations of Vibrationally Resolved Cross Sections and Rate Constants on ab Initio Potential Energy Surfaces for the F + HD Reaction: Comparisons with Experiments

“…1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 2) much more pronounced than in the experiment. The theoretical results simulate correctly the Taipei behavior 49 while showing a much more pronounced maximum for v ′ = 3 in closer agreement with FXZ predictions. As discussed in Ref.…”

Shape resonance in the H + D2O → D + HOD reaction: a full-dimensional quantum dynamics study

“…Since the first theoretical prediction of reaction resonances in the F + H 2 reaction in the early 1970s, 9-11 the search for evidence of such resonances in this reaction has attracted much attention from many top research groups in this field. [12][13][14][15][16][17][18][19][20] Recently, the F + H 2 (HD) reaction was studied extensively in an effort to understand the dynamical resonances in this important system, 8,[21][22][23] using the high-resolution crossed molecular beams technique in combination with full quantum scattering calculation based on accurate potential energy surfaces. The advances made in these studies have provided a clear physical picture of dynamical resonances in this benchmark system that has eluded us for decades.…”