Direct comparison of 3-centre and 4-centre HBr elimination pathways in methyl-substituted vinyl bromides

HBr elimination from energized methyl vinyl bromide molecules can occur through competing 3- and 4-centre transition states.</p

Primary vs. secondary H-atom abstraction in the Cl-atom reaction with n-pentane

Velocity map imaging measurements and quasi-classical trajectory calculations on a newly developed, global potential energy surface combine to reveal the detailed mechanisms of reaction of Cl atoms with n-pentane.</p

Empirical Valence Bond Theory Studies of the CH4 + Cl -> CH3 + HCl Reaction

We report a theoretical investigation of the CH4 + Cl hydrogen abstraction reaction in the framework of empirical valence bond (EVB) theory. The main purpose of this study is to benchmark the EVB method against previous experimental and theoretical work. Analytical potential energy surfaces for the reaction have been developed on which quasi-classical trajectory calculations were carried out. The surfaces agree well with ab initio calculations at stationary points along the reaction path and dynamically relevant regions outside the reaction path. The analysis of dynamical data obtained using the EVB method, such as vibrational, rotational, and angular distribution functions, shows that this method compares well to both experimental measurements and higher-level theoretical calculations, with the additional benefit of low computational cost.status: publishe

Inelastic Scattering of NO by Kr: Rotational Polarization over a Rainbow

We use molecular beams and ion imaging to determine quantum state resolved angular distributions of NO radicals after inelastic collision with Kr. We also determine both the sense and the plane of rotation (the rotational orientation and alignment, respectively) of the scattered NO. By full selection and then detection of the quantum parity of the NO molecule, our experiment is uniquely sensitive to quantum interference. For forward-scattered NO, we report hitherto unseen changes in the plane and sense of rotation with scattering angle and show, remarkably, that the rotation of the NO molecule after collision can be near-maximally oriented for certain transitions and scattering angles. These effects are enhanced by the full parity selection in the experiment and result from the interplay between attractive and repulsive forces