Vibrational branching ratios in photoionization of CO and N2

We report results of experimental and theoretical studies of the vibrational branching ratios for CO 4sigma(-1) photoionization from 20 to 185 eV. Comparison with results for the 2sigma(u)(-1) channel of the isoelectronic N-2 molecule shows the branching ratios for these two systems to be qualitatively different due to the underlying scattering dynamics: CO has a shape resonance at low energy but lacks a Cooper minimum at higher energies whereas the situation is reversed for N-2

Circular dichroism in photoelectron angular distributions from two‐color (1+1) REMPI of NO

A detailed experimental and theoretical study of dichroic effects in photoelectron angular distributions is reported for (1+1), two‐color REMPI of NO via the A^ 2Σ^+, v=0 state. Optically aligned A state rotational levels are probed through ionization by circularly polarized light. Resultant photoelectron angular distributions exhibit significant left–right asymmetry, the phase and magnitude of which are shown to be related to the curvature of the excited state M_J distribution. Theoretical calculations involving a full ab initio treatment of the ionization dynamics result in circularly dichroic angular distribution (CDAD) parameters in good agreement with those derived experimentally. Additional effects including hyperfine depolarization and coherence are also discussed in relation to the observed CDAD data

Studies of electron collisions with polyatomic molecules using distributed-memory parallel computers

Elastic electron scattering cross sections from 5–30 eV are reported for the molecules C_2H_4, C_2H_6, C_3H_8, Si_2H_6, and GeH_4, obtained using an implementation of the Schwinger multichannel method for distributed‐memory parallel computer architectures. These results, obtained within the static‐exchange approximation, are in generally good agreement with the available experimental data. These calculations demonstrate the potential of highly parallel computation in the study of collisions between low‐energy electrons and polyatomic gases. The computational methodology discussed is also directly applicable to the calculation of elastic cross sections at higher levels of approximation (target polarization) and of electronic excitation cross sections

Rotationally resolved threshold photoelectron spectra of OH and OD

The results of combined experimental and theoretical studies of the rotationally resolved photoelectron spectra of OH and OD following single‐photon ionization are presented. The measured zero‐kinetic‐energy (ZEKE) spectra were obtained using pulsed field ionization in conjunction with a vacuum ultraviolet laser source. The OH^+ and OD^+ (X ^3Σ^−, v^+=0) rotational distributions were studied over the range 95.0–95.4 nm. Agreement between the observed and calculated spectra is very encouraging. Improved values for the ionization potentials of OH and OD (104 989 and 105 085 ± 2 cm^(−1), respectively) are reported and the unusual dynamics favoring ΔN<0 transitions are discussed

Absolute Electron Scattering Cross Sections for the CF2 Radical

Using a crossed electron-molecular beam experiment, featuring a skimmed nozzle beam with pyrolytic radical production, absolute elastic cross sections for electron scattering from the CF2 molecule have been measured. A new technique for placing measured cross sections on an absolute scale is used for molecular beams produced as skimmed supersonic jets. Absolute differential cross sections for CF2 are reported for incident electron energies of 30–50 eV and over an angular range of 20–135 deg. Integral cross sections are subsequently derived from those data. The present data are compared to new theoretical predictions for the differential and integral scattering cross sections, as calculated with the Schwinger multichannel variational method using the static-exchange and static-exchange plus polarization approximations

Orientation and substrate interaction of adsorbed CO and NO molecules probed by circular dichroism in the angular distribution of photoelectrons

The sensitivity and utility of circular dichroism in the angular distribution of photoelectrons (CDAD) as a probe of molecular orientation is demonstrated for adsorbed CO and NO molecules. A comparison between measured CDAD spectra and calculated values for spatially oriented CO and NiCO clearly confirms the well-known perpendicular adsorption for CO on Ni(100), whereas for CO adsorbed on Fe(100) a tilted adsorption geometry was found. For NO/Ni(100) and for NO on the oxygen-preadsorbed Ni(100) surface, an average tilt angle of α=40±10° was observed. In the case of the oxygen-preadsorbed Ni(100) surface, a higher fraction of NO molecules was found to be in a tilted orientation than on the clean surface

Low-energy electron scattering from methanol and ethanol

Measured and calculated differential cross sections for elastic (rotationally unresolved) electron scattering from two primary alcohols, methanol (CH3OH) and ethanol (C2H5OH), are reported. The measurements are obtained using the relative flow method with helium as the standard gas and a thin aperture as the collimating target gas source. The relative flow method is applied without the restriction imposed by the relative flow pressure conditions on helium and the unknown gas. The experimental data were taken at incident electron energies of 1, 2, 5, 10, 15, 20, 30, 50, and 100 eV and for scattering angles of 5°–130°. There are no previous reports of experimental electron scattering differential cross sections for CH3OH and C2H5OH in the literature. The calculated differential cross sections are obtained using two different implementations of the Schwinger multichannel method, one that takes all electrons into account and is adapted for parallel computers, and another that uses pseudopotentials and considers only the valence electrons. Comparison between theory and experiment shows that theory is able to describe low-energy electron scattering from these polyatomic targets quite well

Low-energy elastic electron scattering by acetylene

We report measurements and first-principles calculations of the differential cross sections for elastic scattering of low-energy electrons by acetylene, C_2H_2, at collision energies from 1 to 100 eV, with an emphasis on energies near and below that of the π* shape resonance. The measurements cover angles from 5° to 130°. We compare our results to previous experimental and theoretical values

Ion rotational distributions for near-threshold photoionization of H_2O

Ion rotational distributions for single‐photon VUV photoionization of the 1b_1 orbital of the X̃ ^1A_1 ground state of the jet‐cooled water are reported. These spectra reveal significant type a transitions which are seen to arise from odd angular momentum components of the photoelectron matrix element. The resulting photoionization dynamics are quite nonatomic‐like