In this paper we demonstrate that the vector correlation approach for the study of dissociative photoionization (DPI) of linear molecules enables us to achieve a complete description of molecular photoionization by performing a single experiment using only one state of circularly, or elliptically, polarized light. This is illustrated by the derivation of the complex dipole matrix elements for the benchmark DPI reaction of the NO molecule, where (4σ)−1 inner-valence ionization is induced by left-handed circularly polarized synchrotron radiation at hν=23.65 eV. The importance of electronic correlation for this process is emphasized by comparing the experimental results with multichannel Schwinger configuration interaction calculations. The energy dependence of the transition matrix elements and that of the electronic correlation in the 25–40 eV energy range are illustrated by the calculations and compared with the present results and recent experimental studies at 40.8 eV.

Imaging and time-resolved coincidence techniques are combined to determine ion-electron (v-->(i),v-->(e)) velocity correlations in dissociative photoionization of diatomic molecules induced by synchrotron linearly polarized light P-->. The (v-->(i),v-->(e), P-->) vector correlation yields the identification of each process, together with the ( straight theta(e), straight phi(e)) electron emission in the molecule frame for each orientation of the internuclear axis with respect to the polarization. Strong electron emission anisotropies are observed in the NO molecule frame for the parallel and the perpendicular transitions of the NO+hnu(22-25 eV)-->NO+(c(3) Pi)+e-->N+(3P)+O(3P)+e reaction.

The general form of the molecular frame photoelectron angular distributions ͑MFPADs͒ for linear groundstate molecules ionized by linearly polarized light (n ) is reported. A comparison between computed and measured MFPADs as a function of the polar and azimuthal emission angles is presented for photoionization of NO leading to the c 3 ⌸ state of NO ϩ . The importance of the azimuthal dependence of the MFPADs for the determination of the symmetry of the states involved in the excitation and of the underlying photoionization dipole matrix elements is demonstrated.

The interaction of CO 2 with the bare RuO 2 (110) surface, exposing unsaturated Ru and oxygen atoms, was studied using high-resolution electron energy-loss spectroscopy (HREELS) and thermal desorption spectroscopy (TDS). At 85 K, CO 2 is found to adsorb only on coordinatively unsaturated Ru-cus sites giving rise to three different species: physisorbed CO 2 , chemisorbed CO 2 δ-, and CO 2 ‚CO 2 δ-dimers. A complete assignment of the vibrational spectra is reached which allows us to gain insight into the reactions involved. Upon annealing, two channels open up for physisorbed CO 2 : desorption or further reaction with chemisorbed CO 2 δ-forming CO 2 ‚CO 2 δ-dimers. At 175 K, a bidentate carbonate is observed because of the reaction of CO 2 δ-with an O bridge. Further annealing induces a thermally activated conversion from the bidentate to a CO 3 δ-monodentate species. The latter is stable up to about room temperature and then decomposes into CO 2 and O ad . The adsorption geometries of the different species are discussed in detail. The activation of CO 2 to form a chemisorption bond occurs only on the Ru-cus site. This gives further evidence for the key role played by Ru-cus in the catalytic activity of the bare RuO 2 (110) surface.

Aromatic self-assembled monolayers (SAMs) can be used as negative tone electron resists in functional surface lithographic fabrication. A dense and resistant molecular network is obtained under electron irradiation through the formation of a cross-linked network. The elementary processes and possible mechanisms involved were investigated through the response of a model aromatic SAM, p-terphenylthiol SAM, to low-energy electron (0-10 eV) irradiation. Energy loss spectra as well as vibrational excitation functions were measured using High Resolution Electron Energy Loss Spectroscopy (HREELS). A resonant electron attachment process was identified around 6 eV through associated enhanced excitation probability of the CH stretching modes ν(CH)(ph) at 378 meV. Electron irradiation at 6 eV was observed to induce a peak around 367 meV in the energy loss spectra, attributed to the formation of sp(3)-hybridized CHx groups within the SAM. This partial loss of aromaticity is interpreted to be the result of resonance formation, which relaxes by reorganization and/or CH bond dissociation mechanisms followed by radical chain reactions. These processes may also account for cross-linking induced by electron irradiation of aromatic SAMs in general.

A combined experimental and theoretical study of the polar and azimuthal dependence of the molecular frame photoelectron angular distributions (MFPADs) for inner-valence-shell photoionization of the O2 molecule into the O2+(B 2Σg−,3 2Πu,c 4Σu−) states is reported. The measured MFPADs, for each orientation of the molecular axis with respect to the linear polarization of the synchrotron radiation, are derived from the spatial analysis of the (VO+,Ve,P) vector correlation, where the nascent ion and electron velocity vectors VO+ and Ve are determined for each dissociative photoionization (DPI) event using imaging and time of flight resolved coincidence technique as described in the companion paper of this series [J. Chem. Phys. 114, 6605 (2001)]. Expressed in the general form of four FLN(θe) functions which contain all the dynamical information about the photoionization processes, they are compared with the MFPADs computed using the multichannel Schwinger configuration interaction method. A very satisfactory agreement is found. When the lifetime of the O2+ ionic states is a significant fraction of the rotational period, the rotational motion of the molecule is included in the quantal derivation of the MFPADs. Measured MFPADs are also reported for the additional DPI process identified in Paper I, and for DPI involving the excitation of the neutral (3 2Πu,4sσg) Rydberg state.

Dissociative photoionization of H2 induced by VUV linearly polarized synchrotron radiation P has been studied using the (VH+,Ve,P) vector correlation method. The ion–electron kinetic energy correlation diagrams obtained for the three photon excitation energies hν = 20, 28.5 and 32.5 eV enable us to identify and select the dominant dissociative photoionization processes. The Iχ(θe,ϕe) molecular frame photoelectron angular distributions for any orientation χ of the molecular axis with respect to the polarization are reported for direct photoionization of H2 into the H2+(2Σg+) ionic ground state at hν = 20 eV and for the dominant DPI processes involving autoionization of the H2(Q1 1Σu+(1)) and H2(Q2 1Πu(1)) doubly excited states into the H2+(2Σg+) and H2+(2Σu+) continua at hν = 28.5 and 32.5 eV. They show the dominant excitation of a p σu partial wave in autoionization of the Q1(1Σu+(1)) state into the H2+(1s σg) ionic state and that of a d πg partial wave in autoionization of the Q2(1Πu(1)) state into the H2+(2p σu) continuum. A molecular frame forward–backward electron emission anisotropy is observed when ionization takes place at large internuclear distance.

Imaging and time resolved coincidence techniques are combined to determine ion-electron (VO+,Ve,P) velocity vector correlations in dissociative photoionization (DPI) of the O2 molecule induced by linearly polarized synchrotron radiation (P). The ion-electron kinetic energy correlations identify each DPI process by its reaction pathway, intermediate molecular state and dissociation limit. The 4π collection of ions and electrons provides their branching ratios. Up to 12 DPI processes are identified in the 20–28 eV range. Photoionization into the O2+(B 2∑g−) in the Franck–Condon (FC) region populating the [O+(4S)+O(3P)] limit is the dominant process. In the 22.3–24 eV region excitation of the O2*(3 2∏u,nsσg) Rydberg series, followed by dissociation and atomic autoionization to the [O+(2D)+O(3P)] limit reaches about 10% of the DPI flux. A new DPI process is identified in the same energy range, which populates the [O+(4S)+O(1D)] limit. At higher energies the relative weight of the four distinct processes which correspond to ionization into the O2+(3 2∏u) and O2+(c 4∑u−) states in the FC region and population of distinct excited limits is evaluated. The spatial analysis of the (VO+,Ve,P) vector correlation for selected processes will be discussed in a companion paper.