Quantum Dynamics of Oxyhydrogen Complex-Forming Reactions for the HO2 and HO3 Systems

Complex-forming reactions widely exist in gas-phase chemical reactions. Various complexforming bimolecular reactions have been investigated and interesting phenomena have been discovered. The complex-forming reactions usually have small or no barrier in the entrance channel, which leads to obvious differences in kinetic and dynamic characteristics compared with direct reactions. Theoretically, quantum state-resolved reaction dynamics can provide the most detailed microscopic dynamic mechanisms and is now feasible for a direct reaction with only one potential barrier. However, it is of great challenge to construct accurate potential energy surfaces and perform accurate quantum dynamics calculations for a complex polyatomic reaction involving deep potential wells and multi-channels. This paper reviews the most recent progress in two prototypical oxyhydrogen complex-forming reaction systems, HO2 and HO3, which are significant in combustion, atmospheric, and interstellar chemistry. We will present a brief survey of both computational and experimental work and emphasize on some unsolved problems existing in these systems.

Ring Polymer Molecular Dynamics of the C(^(1)D)+H_(2) Reaction on the Most Recent Potential Energy Surfaces

Ring polymer molecular dynamics(RPMD)calculations for the C(^(1)D)+H_(2)reaction are performed on the Zhang-Ma-Bian ab initio potential energy surfaces(PESs)recently constructed by our group,which are unique in very good descriptions of the regions around conical intersections and of van der Waals(vdW)interactions.The calculated reaction thermal rate coefficients are in very good agreement with the latest experimental results.The rate coefficients obtained from the ground˜a^(1)A′ZMB-a PES are much larger than those from the previous RKHS PES,which can be attributed to that the vdW saddles on our PESs have very different dynamical effects from the vdW wells on the previous PESs,indicating that the RPMD approach is able to include dynamical effects of the topological structures caused by vdW interactions.The importance of the excited˜b^(1)A′′ZMB-b PES and quantum effects in the title reaction is also underscored.

van der Waals Interactions in Bimolecular Reactions

The van der Waals (vdW) interaction is very important in fields of physics, biology and chemistry, and its role in reaction dynamics is an issue of great interest. In this review, we focus on the recent progresses in the theoretical and experimental studies on the vdW interaction in bimolecular reactions. In particular, we review those studies that have advanced our understanding of how the vdW interaction can strongly influence the dynamics in both direct activated and complex-forming reactions, and further extend the discussion to the polyatomic reactions involving more atoms and those occurring at cold and ultracold temperatures. We indicate that an accurate description of the delicate vdW structure and long-range potential remains a challenge nowadays in either ab initio calculations or the fitting of the potential energy surfaces. We also present an explanation on the concept of vdW saddle proposed by us recently which may have general importance.

Ab initio Study of Radical-Molecule Reaction： F＋CH2CHCH3

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.

Study on the complex-formation reaction of yttrium with para-methyl-chlorophosphonazo(CPApM)

Yttrium forms with CPApM a 1:2 α-complex instantaneously in acidic medium.At pH～ (buffer solution),the α-complex is transformed to a β-complex with an absorption peak at 755 nm after standing.The transformation reaction is a first-order reaction.The rate constant and the apparent activation energy were found to be 9.67×10^(-) min^(-1) and 52.3 kJ·mol^(-1) respectively.The mechanism of the reaction shows that the β-complex(Y:CPApM=2:4)is formed by combining two molecules of α-complex with the liberation of one proton.