A global three dimensional potential energy surface for the F＋H2→HF＋H reaction has been developed by spline interpolation of about 15,000 symmetry-unique ab initio points, obtained from the multi-reference configuration interaction level with Davidson correction using the aug-cc-pV5Z basis set. In the entrance channel the spin-orbit coupling energy is also included.
Reaction resonance is a frontier topic in chemical dynamics research,and it is also essential to the understanding of mechanisms of elementary chemical reactions.This short article describes an im- portant development in the frontier of research.Experimental evidence of reaction resonance has been detected in a full quantum state resolved reactive scattering study of the F+H2 reaction.Highly accurate full quantum scattering theoretical modeling shows that the reaction resonance is caused by two Feshbach resonance states.Further studies show that quantum interference is present between the two resonance states for the forward scattering product.This study is a significant step forward in our understanding of chemical reaction resonance in the benchmark F+H2 system.Further experimental studies on the effect of H2 rotational excitation on dynamical resonance have been carried out.Dy- namical resonance in the F+H2(j=1)reaction has also been observed.
Quasi-classical trajectory （QCT） calculations on the H^＋＋H2 reaction system were carried out on a new potential energy surface （PES）. Theoretical calculations show that the angular distribution of the forward and backward products is roughly symmetric for the title reaction. The product rotational state distribution was also determined at a few collision energies. In t, he collision energy range from 0.124 eV to 1.424 eV, the integral cross section for this system monotonically decreases with the collision energy. A comparison with the experimental result of the ion-molecule reaction was also made, the agreement is generally good.
The radical-molecule reaction F＋propene （CH2CHCH3） was studied in detail by using the Becke＇s three parameter Lee-Yang-Parr-B3LYP/6-311G（d,p） and coupled cluster with single, double, and triple excitationsCCSD（T）/6-311＋G（2d,2p）. It is shown that F＋propene reaction mainly occurs through complex-formation mechanism： F attacks the double bond of propene leading to the formation of complex 1 and complex 2. As the two radical complexes are metastable, they can quickly dissociate to H＋C3HsF, CH3＋C2H3F and HF＋C3H5. Based on the ab initio calculations, the CH3＋C2H3F is the main channel, and the H elimination and HF forming channels also provide some contribution to products. The calculated values are in good agreement with the recently reported experimental results.
