State-to-state dynamics of the Cl + CH 3 OH → HCl + CH 2 OH reaction Differential cross section polarization moments: Location of the D-atom transfer in the transition-state region for the reactions Cl+C 2 D 6 →DCl (v ′ =0,J ′ =1)+ C 2 D 5 and Cl+CD 4 →DCl (v ′ =0,J ′ =1)+ CD 3The hydrogen atom abstraction reaction between Cl( 2 P 3/2 ) and ethane has been studied at a mean collision energy of 0.24 eV. The experiments were performed in a coexpansion of molecular chlorine and ethane, with the atomic Cl reactants generated by laser photodissociation of Cl 2 at 355 nm. HCl(vЈ, jЈ) products were detected quantum state selectively using (2ϩ1) resonantly enhanced multiphoton ionization, coupled with velocity-map ion imaging. The ion images were used to determine center-of-mass angular and kinetic energy release distributions. Several analysis methods were employed and have been carefully assessed. It is shown that the single beam experiments can be used with confidence to determine both center-of-mass angular and energy release distributions. For the title reaction the angular distribution is found to be forward peaking, with on average 22% of the available energy channeled into internal excitation of the ethyl coproducts. Possible sources of this internal excitation are discussed.

Velocity-map ion imaging, in conjunction with the recently-developed Fourier moment analysis procedure, has been used to determine angular momentum alignment parameters for the Cl( 2 P 3/2 ) products of 308 nm Cl 2 photolysis. The alignment parameters are in good agreement with previous measurements at similar energies and indicate strong alignment of the photofragment orbital angular momentum perpendicular to the recoil direction. The contributions of both adiabatic and non-adiabatic pathways to the dissociation dynamics have been quantified.

An alternative to inverse Abel transform and forward convolution methods is presented for extracting dynamical information from velocity-map ion images. Unlike most competing methods, that presented here does not require the probed three-dimensional distribution to possess cylindrical symmetry. The new method involves analysis of the Fourier moments of images measured in different experimental geometries, and allows speed distributions, angular differential cross sections, and angular momentum alignment and orientation to be determined from raw images of the products of photodissociation and photon-initiated bimolecular reactions. The methodology is developed within the semiclassical framework of Dixon’s bipolar moment formalism [R. N. Dixon, J. Chem. Phys. 85, 1866 (1986)], although it is equally applicable to other common formulations of the product scattering distribution. To allow a comparison of the method with the Abel inversion, which requires that the velocity distribution of the probed product has an axis of cylindrical symmetry, the method is applied to newly acquired experimental images of atomic chlorine produced in the photolysis of NOCl. Extraction of product rotational alignment information is illustrated using newly acquired images of rotationally aligned NO formed by NO2 photolysis. Application of the Fourier moment methodology to studies of bimolecular reactions is also demonstrated, using simulated images for the reaction H+D2→HD(v=0,j=0,9)+D.

Rotational state resolved center-of-mass angular scattering and kinetic energy release distributions have been determined for the HCl (v' = 0, j' = 0-6) products of the reaction of chlorine with n-butane using the photon-initiated reaction technique, coupled with velocity-map ion imaging. The angular and kinetic energy release distributions derived from the ion images are very similar to those obtained previously for the Cl plus ethane reaction. The angular distributions are found to shift from forward scattering to more isotropic scattering with increasing HCl rotational excitation. The kinetic energy release distributions indicate that around 30% of the available energy is channeled into internal excitation of the butyl radical products. The data analysis also suggests that H-atom abstraction takes place from both primary and secondary carbon atom sites, with the primary site producing rotationally cold, forward scattered HCl (v' = 0) products, and the secondary site yielding more isotropically scattered HCl (v' = 0) possessing higher rotational excitation. The mechanisms leading to these two product channels are discussed in the light of the present findings, and in comparison with studies of other Cl plus alkane reactions.

The hydrogen or deuterium atom abstraction reactions between Cl((2)P(3/2)) and methane, or its deuterated analogues CD(4) and CH(2)D(2), have been studied at mean collision energies around 0.34 eV. The experiments were performed in a coexpansion of molecular chlorine and methane in helium, with the atomic Cl reactants generated by polarized laser photodissociation of Cl(2) at 308 nm. The Cl-atom reactants and the methyl radical products were detected using (2+1) resonantly enhanced multiphoton ionization, coupled with velocity-map ion imaging. Analysis of the ion images reveals that in single-beam experiments of this type, careful consideration must be given to the spread of reagent velocities and collision energies. Using the reactions of Cl with CH(4), CD(4), and CH(2)D(2), as examples, it is shown that the data can be fitted well if the reagent motion is correctly described, and the angular scattering distributions can be obtained with confidence. New evidence is also provided that the CD(3) radicals from the Cl+CD(4) reaction possess significant rotational alignment under the conditions of the present study. The results are compared with previous experimental and theoretical works, where these are available.