Born oppenheimer and renner teller quantum dynamics of the ND + D reaction

Hekim, Seda; Akpınar, Sinan

doi:10.1016/j.cplett.2019.05.009

Cited by 1 publication

(1 citation statement)

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“…A more recent theoretical work on the related system ND(a 1 Δ) + D shows that (r) and (e) RT cross sections are closer to those BO than in the previous collisions, because the smaller B and b in eqs and reduce the RT effects in the double deuterated collision. At low E col , ND(a 1 Δ) + D RT cross sections tend to be smaller than the BO ones, while the opposite behavior is found for NH(a 1 Δ) + H. At high E col , ND(a 1 Δ) + D BO and RT cross sections tend to converge even more, contrary to what happens for NH(a 1 Δ) + H. Theoretical and experimental rate constants for ND(a 1 Δ) + D are in better agreement than in the other two isotopic variants, probably because of a better choice of a in eq . This comparison is an example of the great richness that these systems present from a dynamical perspective, which is far from easy to rationalize.…”

Section: Resultsmentioning

confidence: 83%

Quantum Dynamics of Nonadiabatic Renner–Teller Effects in Atom + Diatom Collisions

2021

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We review the quantum nonadiabatic dynamics of atom + diatom collisions due to the Renner–Teller (RT) effect, i.e., to the Hamiltonian operators that contain the total spinless electronic angular momentum L̂. As is well-known, this rovibronic effect is large near collinear geometries when at least one of the interacting states is doubly degenerate. In general, this occurs in insertion reactions and at short-range, where the potential wells exhibit deep minima and support metastable complexes. Initial-state-resolved reaction probabilities, integral cross sections, and thermal rate constants are calculated via the real wavepacket method, solving the equation of motion with an approximated or with an exact spinless RT Hamiltonian. We present the dynamics of 10 single-channel or multichannel reactions showing how RT effects depend on the product channels and comparing with the Born–Oppenheimer (BO) approximation or coexisting conical-intersection (CI) interactions. RT effects not only can significantly modify the adiabatic dynamics or correct purely CI results, but also they can be very important in opening collision channels which are closed at the BO or CI level, as in electronic-quenching reactions. In the OH(A2Σ+) + Kr electronic quenching, where both nonadiabatic effects (CI and RT) coexist, they are in competition because CI dominates the reactivity but RT couplings reduce the large CI cross section and open a CI-forbidden evolution toward products, so that CI + RT quantum results are in good agreement with experimental or semiclassical findings. The different roles of these couplings are due to the unlike nuclear geometries where they are large: rather far from or near to linearity for CI or RT, respectively. The OH(A2Σ+) + Kr electronic quenching was investigated with the exact RT Hamiltonian, validating the approximated one, which was employed for all other collisions.

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Section: Resultsmentioning

confidence: 83%