State-to-state dynamics of the Cl(2P) + C2H6(ν5, ν1 = 0, 1) → HCl(v′, j′) + C2H5 hydrogen abstraction reactions

When Classical Trajectories Get to Quantum Accuracy: The Scattering of H2on Pd(111)

“…[1][2][3][4][5][6][7][8][9][10] For chemical reactions involving a small number of degrees-of-freedom (DOF) (typically less than or equal to 6), quantum dynamics calculations might be now regarded as exact since they generally provide results in excellent agreement with experiments. 11,12 However, reaction dynamics studies focus on systems of ever increasing size [13][14][15][16][17][18][19][20][21][22][23][24][25][26][27][28] for which the quasi-classical trajectory (QCT) method is at this time the only practical tool to apply. A crucial issue is thus to develop theoretically justified corrections to carry out classical dynamics studies of chemical reactions in a quantum spirit.…”

“…In the last five decades, synergetic advances in theory and molecular beam experiments associated with a tremendous increase of computing power have allowed a detailed understanding of the dynamics of chemical elementary processes, particularly through the study of state-to-state reaction and/or inelastic probabilities. − For chemical reactions involving a small number of degrees-of-freedom (DOF) (typically less than or equal to 6), quantum dynamics calculations might be now regarded as exact because they generally provide results in excellent agreement with experiments. , However, reaction dynamics studies focus on systems of ever increasing size ,− for which at this time the quasi-classical trajectory (QCT) method is the approach predominantly used to calculate state-to-state probabilities. A crucial issue is thus to develop semiclassical tools which, coupled with the QCT method, make its predictions more realistic when major quantum effects come into play in the dynamics .…”

Advances and New Challenges to Bimolecular Reaction Dynamics Theory

“…In the so-called sudden vector projection (SVP) model, the ability of a reactant mode in promoting the reaction depends on its coupling with the reaction coordinate at the transition state, which can be estimated in the sudden limit by the overlap of their corresponding normal mode vectors . The SVP model, which emphasizes the importance of the transition state in controlling reactivity, has been tested in many reactions, including some recent ones, ,− and its predictions have mostly been borne out. ,, The SVP model is not only able to predict mode specificity in reactions involving only a few atoms; it has been also validated in larger systems. For example, the Diels–Alder reaction between 2,3-dibromo-1,3-butadiene and maleic anhydride was found to be enhanced by exciting reactant rotational DOFs, in line with the prediction of SVP .…”

Mode specificity of a multi-channel reaction prototype: F + CH3OH → HF + CH3O/CH2OH

“…Theoretically, using either quasi-classical trajectories (QCT) or quantum dynamics (QD) on full-dimensional accurate potential energy surfaces (PESs), ample investigations have been carried out on the mode-specific chemistry in various chemical reactions, such as H/O/F/Cl/OH + H 2 O/ CH 4 (and their isotopologs) , OH/OD + GeH 4 [33], Cl + C 2 H 6 [34,35], OH + HO 2 [36], the SN 2 reactions F − + CH 3 Cl [37,38] and F − + CH 3 I [39], H + NH 3 [40], H + H 2 S [41][42][43]. Based on ample studies of atom-diatom reactions, Polanyi summarized that: for exothermic reactions with an "early barrier," the translation motion is more effective to enhance the reactivity than the vibrational motion, whereas the reactant vibration would be more effective for endothermic reactions with a "late barrier" [44,45].…”