Optical control of ground-state atomic orbital alignment: Cl(2P3/2) atoms from HCl(v=2,J=1) photodissociation.

H(35)Cl(v=0,J=0) molecules in a supersonic expansion were excited to the H(35)Cl(v=2,J=1,M=0) state with linearly polarized laser pulses at about 1.7 microm. These rotationally aligned J=1 molecules were then selectively photodissociated with a linearly polarized laser pulse at 220 nm after a time delay, and the velocity-dependent alignment of the (35)Cl((2)P(32)) photofragments was measured using 2+1 REMPI and time-of-flight mass spectrometry. The (35)Cl((2)P(32)) atoms are aligned by two mechanisms: (1) the time-dependent transfer of rotational polarization of the H(35)Cl(v=2,J=1,M=0) molecule to the (35)Cl((2)P(32)) nuclear spin [which is conserved during the photodissociation and thus contributes to the total (35)Cl((2)P(32)) photofragment atomic polarization] and (2) the alignment of the (35)Cl((2)P(32)) electronic polarization resulting from the photoexcitation and dissociation process. The total alignment of the (35)Cl((2)P(32)) photofragments from these two mechanisms was found to vary as a function of time delay between the excitation and the photolysis laser pulses, in agreement with theoretical predictions. We show that the alignment of the ground-state (35)Cl((2)P(32)) atoms, with respect to the photodissociation recoil direction, can be controlled optically. Potential applications include the study of alignment-dependent collision effects.

Comparing reactions of H and Cl with C-H stretch-excited CHD3.

We report the methyl radical product state distributions for the reactions of H and Cl with CHD3(nu1 = 1,2) at collision energies of 1.53 and 0.18 eV, respectively. Both reactions demonstrate mode selectivity. The resulting state distributions from the H+CHD3(nu1 = 1,2) reactions are well described by a spectator model. The reactions Cl + CHD3(nu1 = 1,2) exhibit similar behavior, but in some aspects the spectator model breaks down. We attribute this breakdown to enhanced intramolecular vibrational redistribution in the Cl + CHD3(nu1 = 1,2) reactions compared to the H + CHD3(nu1 = 1,2) reactions, caused by the interaction of the slower Cl atom with the vibrationally excited CHD3, which is promoted either by its longer collision duration, its stronger coupling, or both.

A reinterpretation of the mechanism of the simplest reaction at an sp3-hybridized carbon atom: H + CD4 --> CD3 + HD.

A comparison between theory and experiment for the benchmark H + CD4 --> HD + CD3 abstraction reaction yields a reinterpretation of the reaction mechanism and highlights the unexpected contribution of a stripping mechanism. Whereas the best analytic surface fails to reproduce experiment, a first-principles direct-dynamics (on the fly) treatment is in good agreement, showing that the H + CD4 reaction exhibits extreme sensitivity to modest differences in the potential energy surface. We find that bent H-D-C transition state geometries play an important role in the dynamics. A simple model that relates the scattering angle impact parameter and cone of acceptance accounts well for the overall reaction dynamics.