Resonances in the O(3P)+HCl reaction due to van der Waals minima

Abstract

Quantum scattering calculations of the O ( 1 D)+ HCl reaction using a new ab initio potential and extensions of Jshifting J.Quantum reaction dynamics of O ( 3 P) +HCl on a new ab initio potential energy surface Dynamics of the O ( 3 P)+ HCl reaction on the 3 A ″ electronic state: A new ab initio potential energy surface, quasi-classical trajectory study, and comparison to experimentWe present extensive exact quantum calculations of the cumulative reaction probability ͑CRP͒ for the O( 3 P)ϩHCl→OHϩCl reaction for a large range of total angular momentum, using the most recent ab initio potential energy surface of Ramachandran et al. This surface contains van der Waals minima in both the entrance and exit channels that are shown to be responsible for a number of prominent resonances in the CRP in the tunneling region. The evidence for this claim is based on an analysis of the quasibound states of the van der Waals minima and a simple overlap of these states with the region of the saddle point of the reaction. The shift of the CRP with total angular momentum is analyzed in detail, with a focus on the resonances. A rigorous test of the simple J -K shifting approximation is also made both for the total CRP and the thermal rate constant.

Ab Initio Treatment of the Chemical Reaction Precursor Complex Br(2P)−HCN. 2. Bound-State Calculations and Infrared Spectra

“…[1][2][3][4][5][6] The complex Cl( 2 P)-HF that occurs in the entrance channel of the reaction Cl + HF f F + HCl was recently prepared in helium nanodroplets and studied by high-resolution infrared laser spectroscopy. 7 The preceding paper 8 describes the ab initio calculation and analytic representation of the full 3 × 3 matrix of diabatic potentials required to compute the bound states of this complex with the inclusion of the nonadiabatic Renner-Teller coupling.…”

Potential energy surfaces and bound states for the open-shell van der Waals cluster Br–HF

“…Atomic Br has a 2 P ground state with the configuration ͓Ar͔(3d) 10 (4s) . Since the z axis is the interatomic axis, the first two of these are degenerate and form a ⌸ state with potential curve V ⌸ (R), while the third forms a ⌺ state with potential curve V ⌺ (R).…”

“…For example, Maierle et al 6 and Dobbyn et al 7 have developed full reactive potentials for Cl-HCl that incorporate the Dubernet-Hutson potential at long range, and these have been used to show that the long-range well has important effects on the positions of reactive scattering resonances and to calculate thermal rate coefficients. 8,9 Xie et al 10 have shown that long-range forces are responsible for prominent resonances in the O ( 3 P)ϩHCl reaction, while Skouteris et al 11 have shown that such forces play a decisive role in determining the product isotope ratio in the ClϩHD reaction.…”

Reactive resonances in the N+N2 exchange reaction

“…Very recently these reactive resonances have been observed in experimental studies of these reactions, H + D2 + HD +D [6], H + HD + D + H2 [7] and F + HD -+ HF + D [8]. There The second is the result of quasibound states localized in the van der Waals well of either the entrance or exit channel, such as the resonances in 0 + HC1 reaction [9]. The third type occurs when the reacting system has a chemically bound state with a barrier to the asymp- The first quantum dynamics study of the cumulative reaction probabilities and chemical reaction rates of the N+N2 exchange reaction, as well as the first ab initio potentia1 energy surface(PES) for the N3 system, have been reported by this group [ll].…”

“…!PFi(E, R) is the scattering wave funct ion. complex Hamiltonian matrix using the L2 method with an absorbing potential in the reactant channel [9]. The stationary eigenvalues are identified as be the quasibound states, and the real and imaginary parts of these eigenvalues give the resonance energies and widths.…”