Stereo-specific reaction mechanisms play a fundamental role in chemistry. The back-side attack inversion and front-side attack retention pathways of the bimolecular nucleophilic substitution (S N 2) reactions are the textbook examples for stereo-specific chemical processes. Here, we report an accurate global analytic potential energy surface (PES) for the F À þ CH 3 Cl S N 2 reaction, which describes both the back-side and front-side attack substitution pathways as well as the proton-abstraction channel. Moreover, reaction dynamics simulations on this surface reveal a novel double-inversion mechanism, in which an abstraction-induced inversion via a FH Á Á Á CH 2 Cl À transition state is followed by a second inversion via the usual [F Á Á Á CH 3 Á Á Á Cl] À saddle point, thereby opening a lower energy reaction path for retention than the front-side attack. Quasi-classical trajectory computations for the F À þ CH 3 Cl(n 1 ¼ 0, 1) reactions show that the front-side attack is a fast direct, whereas the double inversion is a slow indirect process.
There has been great progress in the development of potential energy surfaces (PESs) for reaction dynamics that are fits to ab initio energies. The fitting techniques described here explicitly represent the invariance of the PES with respect to all permutations of like atoms. A review of a subset of dynamics calculations using such PESs (currently 16 such PESs exist) is then given. Bimolecular reactions of current interest to the community, namely, H + CH(4) and F + CH(4), are focused on. Unimolecular reactions are then reviewed, with a focus on the photodissociation dynamics of H(2)CO and CH(3)CHO, where so-called "roaming" pathways have been discovered. The challenges for electronically non-adiabatic reactions, and associated PESs, are presented with a focus on the OH* + H(2) reaction. Finally, some thoughts on future directions and challenges are given.
We report quasiclassical trajectory (QCT) calculations of the correlated product distributions and branching ratios of the reactions F+CHD(3)(v(1)=0,1)-->HF(v)+CD(3)(v) and DF(v)+CHD(2)(v) using a recently published ab initio-based full-dimensional global potential energy surface [G. Czako et al., J. Chem. Phys. 130, 084301 (2009)]. Harmonic normal mode analysis is done for the methyl products to determine the classical actions of each normal mode and then standard histogram binning and Gaussian binning (GB) methods are employed to obtain quantum state-resolved probabilities of the products. QCT calculations have been performed for both the vibrationally ground state and the CH stretching excited F+CHD(3)(v(1)=0,1) reactions at eight different collision energies in the 0.5-7.0 kcal/mol range. HF and DF vibrationally state-resolved rotational and angular distributions, CD(3) and CHD(2) mode-specific vibrational distributions, and correlated vibrationally state-specific distributions for the product pairs have been obtained and the correlated results were compared to the experiment. We find that the use of GB can be advantageous especially in the threshold regions. The CH stretching excitation in the reactant does not change the CD(3) vibrational distributions significantly, whereas the HF molecules become vibrationally and rotationally hotter. On the other hand in the case of the DF+CHD(2) channel the initially excited CH stretch appears mainly "intact" in the CHD(2) product and the DF distributions are virtually the same as formed from the ground state CHD(3) reaction. The computed results qualitatively agree with recent crossed molecular beam experiment [W. Zhang et al., Science 325, 303 (2009)] that (a) CHD(2)(v(1)=1) is the most populated product state of the F+CHD(3)(v(1)=1) reaction and this reaction produces much less CHD(2)(v=0) compared to the reaction F+CHD(3)(v=0); (b) the cross section ratio of CHD(2)(v(1)=1):CHD(2)(v=0) formed from the reactions F+CHD(3)(v(1)=1):F+CHD(3)(v=0) is less than 1 and shows little collision energy dependency; (c) the reactant CH stretch excitation increases the DF:HF ratio at low collision energies; (d) the correlated vibrational and angular distributions for DF(v)+CHD(2)(v(1)=0,1) from the ground state and stretch-excited reactions, respectively, are almost identical.
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