Mass-analyzed threshold ionization spectroscopy of lanthanum-hydrocarbon radicals formed by C-H bond activation of propene.

La(C3H4) and La(C3H6) are observed from the reaction of laser-vaporized La atoms with propene by photoionization time-of-flight mass spectrometry and characterized by mass-analyzed threshold ionization spectroscopy. Two isomers of La(C3H4) are identified as methyl-lanthanacyclopropene [La(CHCCH3)] (Cs) and lanthanacyclobutene [La(CHCHCH2)] (C1); La(C3H6) is determined to be H-La(η3-allyl) (Cs), a C-H bond inserted species. All three metal-hydrocarbon radicals prefer a doublet ground state with a La 6s-based electron configuration. Ionization of the neutral doublet state of each of these radicals produces a singlet ion state by removing the La-based 6s electron. The threshold ionization allows accurate measurements of the adiabatic ionization energy of the neutral doublet state and metal-ligand and ligand-based vibrational frequencies of the neutral and ionic states. The formation of the three radicals is investigated by density functional theory computations. The inserted species is formed by La inserting into an allylic C-H bond and lanthanacyclopropene by concerted vinylic H2 elimination, whereas lanthanacyclobutene involves both allylic and vinylic dehydrogenations. The inserted species is identified as an intermediate for the formation of lanthanacyclobutene.

Photodissociation of heptane isomers and relative ionization efficiencies of butyl and propyl radicals at 157 nm.

We report an ion imaging and time-of-flight mass spectroscopy study of the photodissociation of a variety of heptane isomers using 157 nm dissociation and ionization. Time-of-flight mass spectra show that C(3)H(7) + C(4)H(9) is the dominant detected product channel following one-color 157 nm dissociation/ionization of heptanes. The results further allow determination of the relative ionization efficiencies of 1- and 2-butyl and propyl radicals at 157 nm. Momentum matching for the two radical products indicates that, for the C3-C4 products, neutral dissociation followed by ionization is the main source of the detected signals. The images show isotropic angular distributions and the translational energy distributions peak at very low energy, with only approximately 0.3 eV or 8% of the available energy appearing in translation. This is consistent with dissociation from the ground state or low-lying triplet states following non-radiative electronic relaxation.

Photodissociation of spatially aligned acetaldehyde cations.

Photofragment translational energy and angular distributions are reported for the photodissociation of acetaldehyde cations in the wavelength range 354-363 nm obtained using the DC slice ion imaging technique. Vibrationally selected parent ions were produced by 2+1 resonance-enhanced multiphoton ionization (REMPI) via the 3s<--n Rydberg transition, with photodissociation resulting from absorption of a fourth additional photon. Three product channels were observed: HCO+, CH3CO+, and CH4+. The angular distributions reveal that all product channels have a predominantly parallel recoil anisotropy although the lower beta2 parameter of CH3CO+ indicates the concomitant presence of a perpendicular component. Furthermore, the distinct angular distribution of the CH3CO+ fragments shows a large value of the higher order Legendre polynomial term, providing evidence that acetaldehyde cations are spatially aligned during the ionization process.

S(1D2) atomic orbital polarization in the photodissociation of OCS at 193 nm: Construction of the complete density matrix.

The absolute velocity-dependent alignment and orientation for S(1D2) atoms from the photodissociation of OCS at 193 nm were measured using the dc slice imaging method. Three main peaks ascribed to specific groups of high rotational levels of CO in the vibrational ground state were found, with rotationally resolved rings in a fourth slow region ascribed to weak signals associated with excited vibrational states of CO. The observed speed-dependent beta and polarization parameters support the interpretation that there are two main dissociation processes: a simultaneous two-surface (A' and A") excitation and the initial single-surface (A') excitation followed by the nonadiabatic crossing to ground state. At 193 nm photodissociation, the nonadiabatic dissociation process is strongly enhanced relative to longer wavelengths. The angle- and speed-dependent S(1D2) density matrix can be constructed including the higher order (K = 3,4) contributions for the circularly polarized dissociation light. This was explicitly done for selected energies and angles. It was found in one case that the density matrix is sensitively affected by the rank 4 terms, suggesting that the higher order contributions should not be overlooked for an accurate picture of the dissociation dynamics in this system.