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The stereodynamics of the Penning ionization of water molecules by collision with metastable neon atoms, occurring in the thermal energy range, is of great relevance for the understanding of fundamental aspects of the physical chemistry of water. This process has been studied by analyzing the energy spectrum of the emitted electrons previously obtained in our laboratory in a crossed beam experiment [B. G. Brunetti, P. Candori, D. Cappelletti, S. Falcinelli, F. Pirani, D. Stranges, and F. Vecchiocattivi, Chem. Phys. Lett. 539-540, 19 (2012)]. For the spectrum analysis, a novel semiclassical method is proposed, that assumes ionization events as mostly occurring in the vicinities of the collision turning points. The potential energy driving the system in the relevant configurations of the entrance and exit channels, used in the spectrum simulation, has been formulated by the use of a semiempirical method. The analysis puts clearly in evidence how different approaches of the metastable atom to the water molecule lead to ions in different electronic states. In particular, it provides the angular acceptance cones where the selectivity of the process leading to the specific formation of each one of the two energetically possible ionic product states of H2O(+) emerges. It is shown how the ground state ion is formed when neon metastable atoms approach water mainly perpendicularly to the molecular plane, while the first excited electronic state is formed when the approach occurs preferentially along the C2v axis, on the oxygen side. An explanation is proposed for the observed vibrational excitation of the product ions.

The double photoionization of HI molecules has been investigated using vacuum ultraviolet synchrotron radiation in the energy range between 27 and 35 eV. The product ions have been detected by the use of time-of-flight mass spectrometry and the threshold energy for HI2+ and H+ + I+ formation has been determined. These results have been interpreted by the use of a theoretical model which has been previously applied by us to HBr2+ and HCl2+. On the basis of the reliability of such a model, an assessment of the systematic trends of the bond features along the HX2+ (X=F, Cl, Br, I) homologous series is given in this paper. In particular, the increase of the stability of these dications, in their lowest electronic states, when going towards the heavier molecules, has been rationalized considering the systematic variation of the charge transfer coupling between the H-X2+ and the H+-X+ states.

A theoretical investigation of the intermolecular interaction, operative in collision complexes of He*(2 3S1), He*(2 1S0), and Ne*(3P2,0) with N2O, is carried out to explain the main results of the experimental study reported in the preceding paper. The analysis is carried out by means of a semiempirical method based on the identification, modeling, and combination of the leading interaction components, including the effect of the selective polarization of the more external electronic cloud of the metastable atom in the intermolecular electric field. These and other crucial aspects of our approach have been quantitatively verified by ab initio calculations. The proposed method permits to evaluate the interaction at any configuration of the complexes and provides a useful and inexpensive representation of the intermolecular potential energy for dynamics studies. The main experimental findings can be rationalized taking into account the critical balancing between molecular orientation effects in the intermolecular interaction field and the ionization probability. These orientation effects tend to become less pronounced with increasing collision energy.

The energetics of [Rg... N2O]* autoionizing collision complexes (where Rg=He or Ne) and their dynamical evolution have been studied in a crossed beam apparatus, respectively, by Penning ionization electron spectroscopy (PIES) and by mass spectrometry (MS) techniques in the thermal energy range. The PIES spectra, detected by an electron energy analyzer, were recorded for both complexes at four different collision energies. Such spectra allowed the determination of the energy shifts for Penning electron energy distributions, and the branching ratios for the population of different electronic states and for the vibrational population in the molecular nascent ions. For the [Ne...N2O]* collision complex it was found, by MS, that the autoionization leads to the formation of N2O+, NO+, O+, and NeN2O+ product ions whose total and partial cross sections were measured in the collision energy range between 0.03 and 0.2 eV. The results are analyzed exploiting current models for the Penning ionization process: the observed collision energy dependence in the PIES spectra as well as in the cross sections are correlated with the nature of the N2O molecule orbitals involved in the ionization and are discussed in term of the Rg-N2O interaction potentials, which are estimated by using a semiempirical method developed in our laboratory.

The double photoionization of HCl molecules by synchrotron radiation has been studied in the energy range between 30 and 50 eV. The HCl(2+) and Cl(2+) product ions have been detected by a photoelectron-photoion-coincidence technique, while the H(+)+Cl(+) formation, which follows the double ionization of HCl, has been studied by photoelectron-photoion-photoion coincidence. The photon energy threshold for the production of HCl(2+) ions has been found to be 35.4+/-0.6 eV, while for the dissociative channel leading to H(+)+Cl(+), it has been measured a threshold at 36.4+/-0.6 eV and a change in the slope of the cross-section energy dependence at 38.7+/-0.7 eV. The production of H+Cl(2+) occurs with a threshold photon energy of 42.8+/-1.1 eV. These results appear to be in a good agreement with previous data by different experimental techniques and recent theoretical calculations performed by our laboratory., ((c) 2004 American Institute of Physics.)

The present study describes the characterization of energy and structure of HBr(2+) in its low-lying electronic states, achieved through an extension of a new empirical method [Chem. Phys. Lett. 379, 139 (2003)] recently introduced to evaluate the interatomic interaction in the HX(2+) (X=F,Cl,Br,I) molecular dications. The method is based on identification of the main components of the interaction and their evaluation through some simple correlation formulas. Potential energy curves, given in a simple, natural, and analytical form, made possible the calculations of some important properties, such as double-photoionization energy thresholds, vibrational spacing, average lifetime, and Franck-Condon factors. The predictions, compared with data available in the literature, are of great interest for the analysis and interpretation of some new experimental results., ((c) 2004 American Institute of Physics.)

A threshold-photoelectron-coincidence spectrum of HBr has been recorded in the 32.2-35.8 eV photon energy range, with a resolution of approximately 0.01 eV, using a synchrotron radiation source. The X (3)Sigma(-) and a (1)Delta(2) states of the HBr(2+) dication are clearly observed in the spectrum, while there is no clear evidence for the formation of the b (1)Sigma(+) electronic state. For the first two states, the vibrational states v=0-3 have been resolved, while for the ground X (3)Sigma(-) state also spin-orbit splitting has been detected. The results appear in good agreement with previous experimental observations. A comparison with theoretical predictions indicates the role of "noncovalent" contributions to the interaction between the two atomic partners for the formation of metastable states., ((c) 2004 American Institute of Physics.)