Communication: Experimental and theoretical investigations of the effects of the reactant bending excitations in the F+CHD3 reaction

Abstract

The effects of the reactant bending excitations in the F+CHD3 reaction are investigated by crossed molecular beam experiments and quasiclassical trajectory (QCT) calculations using a high-quality ab initio potential energy surface. The collision energy (Ec) dependence of the cross sections of the F+CHD3(vb=0,1) reactions for the correlated product pairs HF(v′)+CD3(v2=0,1) and DF(v′)+CHD2(v4=0,1) is obtained. Both experiment and theory show that the bending excitation activates the reaction at low Ec and begins to inactivate at higher Ec. The experimental F+CHD3(vb=1) excitation functions display surprising peak features, especially for the HF(v′=3)+CD3(v2=0,1) channels, indicating reactive resonances (quantum effects), which cannot be captured by quasiclassical calculations. The reactant state-specific QCT calculations predict that the v5(e) bending mode excitation is the most efficient to drive the reaction and the v6(e) and v5(e) modes enhance the DF and HF channels, respectively.

A full-dimensional wave packet dynamics study of the photodetachment spectra of ${\rm FCH}_{4}^{-}$ FCH 4−

“…ten years, advances in reactive scattering experiments have uncovered many details of the dynamics of the F + CH 4 → HF + CH 3 reaction. [16][17][18][19][20][21][22][23][24][25][26][27][28][29][30] These advances have allowed, for example, to describe its mode-selected chemistry [26][27][28] and mode-specific dynamics 17,28 to a good extent. Moreover, it has been possible to determine the correlation between the final states of the co-products, shedding light about the way in which different modes of motion interact with each other and with the motion along the reaction path.…”

Resonances in the Entrance Channel of the Elementary Chemical Reaction of Fluorine and Methane

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Extending the fully quantum-state-resolved description of elementary chemical reactions beyond three or four atom systems is a crucial issue in fundamental chemical research. Full-dimensional potentialenergy surfaces (PESs) based on high-level ab initio calculations have been constructed, [8,[10][11][12] and quantum-state-resolved reaction dynamics on these surfaces have been studied by quasi-classical trajectory simulations, which cannot describe resonances [4,[11][12][13] and reduced-dimensional wavepacket calculations. In particular, reactive resonances and nonintuitive mode-selective chemistry have been reported in experimental studies for the F + CH 4 !

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Communication: Probing the entrance channels of the X + CH4 → HX + CH3 (X = F, Cl, Br, I) reactions via photodetachment of X−–CH4

“…This work complements the beautiful crossed molecular beam studies of the F + CH 4 and Cl + CH 4 reactions. [14][15][16][17][18][19] Furthermore, our work presents the first characterization of the seemingly similar Br and I + CH 4 reactions.…”