Double Photoionization of Nitrosyl Chloride by Synchrotron Radiation in the 24-70 eV Photon Energy Range.

The behavior of nitrosyl chloride (ClNO) exposed to ionizing radiation was studied by direct probing valence-shell electrons in temporal coincidence with ions originating from the fragmentation process of the transient ClNO. Such a molecular dication was produced by double photoionization with synchrotron radiation in the 24-70 eV photon energy range. The experiment has been conducted at the Elettra Synchrotron Facility of Basovizza (Trieste, Italy) using a light beam linearly polarized with the direction of the polarization vector parallel to the ClNO molecular beam axis.

The role of precursor states in the stereo-dynamics of elementary processes.

The present perspective review focuses on the role of the precursor state, controlling the dynamical evolution of elementary processes, whose structure and stability are often difficult to characterize on quantitative grounds. In particular, such a state depends on the critical balance of weak intermolecular forces operative at long and intermediate separation distances. In this paper, a complementary problem has been properly addressed, concerning the suitable formulation of the intermolecular forces involved, defined in terms of a limited number of parameters and applicable in the whole space of the relative configurations of interacting partners.

The topology of the reaction stereo-dynamics in chemi-ionizations.

Details on the stereo-dynamic topology of chemi-ionizations highlight the role of the centrifugal barrier of colliding reactants: it acts as a selector of the orbital quantum number effective for reaction in a state-to-state treatment. Here, an accurate internally consistent formulation of the Optical interaction potentials, obtained by the combined analysis of scattering and spectroscopic experimental findings, casts light on structure, energy and angular momentum couplings of the precursor (pre-reactive) state controlling the stereo-dynamics of prototypical chemi-ionization reactions. The closest approach (turning point) of reagents, is found to control the relative weight of two different reaction mechanisms: (i) A direct mechanism stimulated by exchange chemical forces mainly acting at short separation distances and high collision energy; (ii) An indirect mechanism, caused by the combination of weak chemical and physical forces dominant at larger distances, mainly probed at low collision energy, that can be triggered by a virtual photon exchange between reagents.

Basic features of Ne*-HX (X = Cl, Br) chemi-ionization reactions.

Total and partial ionization cross sections for Ne*(P)-HX (X = Cl, Br) are presented in a comparative way as a function of the collision energy between 0.02-0.5 eV.

Selectivity of weak intermolecular forces and precursor state of elementary oxidation reactions, a new insight on Ne + N chemiionization.

This paper reports on the collision dynamics of N with metastable Ne promoting chemiionizations, prototype of barrier-less oxidation reactions of great interest for fundamental and applied research. Extending guidelines presented in previous papers for the atom-atom case, an innovative treatment of the reaction stereodynamics involving molecules in a quantum state-to-state resolution conditions is proposed that emphasizes the role of structure and stability of the precursor that is here the reaction transition state. A critical test of such treatment, carried out exploiting a new formulation both of real and imaginary parts of the optical potential driving the reaction dynamics, is represented by the detailed-combined description of all relevant findings, provided by high resolution molecular beam scattering experiments carried out in our and other laboratories.

Chemi-Ionization Reactions and Basic Stereodynamical Effects in Collisions of Atom-Molecule Reagents.

A new theoretical method, developed by our laboratory to describe the microscopic dynamics of gas-phase elementary chemi-ionization reactions, has been applied recently to study prototype atom-atom processes involving reactions between electronically excited metastable Ne*(P) and heavier noble gas atoms. Important aspects of electronic rearrangement selectivity have been emphasized that suggested the existence of two fundamental microscopic reaction mechanisms. The distinct mechanisms, which are controlled by intermolecular forces of chemical and noncovalent nature respectively, emerge under different conditions, and their balance depends on the collision energy regime investigated.

Electronic Rearrangements and Angular Momentum Couplings in Quantum State-to-State Channels of Prototype Oxidation Processes.

An innovative theoretical method to describe the microscopic dynamics of chemi-ionization reactions as prototype oxidation processes driven by selective electronic rearrangements has been recently published. It was developed and applied to reactions of Ne* atoms excited in their metastable P state, and here, its physical background is extensively described in order to provide a clear description of the microscopic phenomenon underlying the chemical reactivity of the oxidative processes under study. It overcomes theoretical models previously proposed and reproduces experimental results obtained in different laboratories.

Quantum-State Controlled Reaction Channels in Chemi-ionization Processes: Radiative (Optical-Physical) and Exchange (Oxidative-Chemical) Mechanisms.

ConspectusMost chemical processes are triggered by electron or charge transfer phenomena (CT). An important class of processes involving CT are chemi-ionization reactions. Such processes are very common in nature, involving neutral species in ground or excited electronic states with sufficient energy (X*) to yield ionic products, and are considered as the primary initial step in flames.

General treatment for stereo-dynamics of state-to-state chemi-ionization reactions.

The investigation of chemi-ionization processes provides unique information on how the reaction dynamics depend on the energy and structure of the transition state which relate to the symmetry, relative orientation of reagent/product valence electron orbitals, and selectivity of electronic rearrangements. Here we propose a theoretical approach to formulate the optical potential for Ne*(P) noble gas atom chemi-ionizations as prototype oxidation processes. We include the selective role of atomic alignment and of the electron transfer mechanism.

Angular Distribution of Ion Products in the Double Photoionization of Propylene Oxide.

A photoelectron-photoion-photoion coincidence technique, using an ion imaging detector and tunable synchrotron radiation in the 18.0-37.0 eV photon energy range, inducing the ejection of molecular valence electrons, has been applied to study the double ionization of the propylene oxide, a simple prototype chiral molecule.

A New Insight on Stereo-Dynamics of Penning Ionization Reactions.

Recent developments in the experimental study of Penning ionization reactions are presented here to cast light on basic aspects of the stereo-dynamics of the microscopic mechanisms involved. They concern the dependence of the reaction probability on the relative orientation of the atomic and molecular orbitals of reagents and products. The focus is on collisions between metastable Ne(P) atoms with other noble gas atoms or molecules, for which play a crucial role both the inner open-shell structure of Ne and the HOMO orbitals of the partner.

The electron couplings in the transition states: The stereodynamics of state to state autoionization processes.

Measurements of the kinetic energy distribution of electrons, emitted in collision between Ne(P) and Kr(S) and Xe(S), have been performed in a crossed molecular beam apparatus which employs a mass spectrometer and a hemispherical electron analyzer as detectors. The analysis of the obtained experimental results provides new insights on electronic rearrangements and electronic angular momentum coupling effects that determine relevant properties of the transition state of autoionization processes, and that we have found useful to classify as adiabatic and non-adiabatic effects. In particular, while the adiabatic effects control sequence, energy, and symmetry of quantum states accessible to both reagents and products in the probed collision energy range, the non-adiabatic ones trigger the passage from entrance to exit channels.

Adiabatic and Nonadiabatic Effects in the Transition States of State to State Autoionization Processes.

The energy distribution of electrons, emitted from collisions between Ne^{*}(^{3}P_{2,0}) and Kr(^{1}S_{0}), have been measured under high resolution conditions in a crossed molecular beam apparatus containing a hemispherical electron analyzer as detector. The experimental results provide new insights on the electronic adiabatic and nonadiabatic effects in the stereodynamics of state to state atomic and molecular collisions, controlling relevant properties of the transition state of autoionization processes. In particular, while the adiabatic effects determine sequence, energy, and symmetry of quantum states accessible both to reagents and products, the nonadiabatic effects trigger the passage from entrance to exit channels.

Double photoionization of propylene oxide: A coincidence study of the ejection of a pair of valence-shell electrons.

Propylene oxide, a favorite target of experimental and theoretical studies of circular dichroism, was recently discovered in interstellar space, further amplifying the attention to its role in the current debate on protobiological homochirality. In the present work, a photoelectron-photoion-photoion coincidence technique, using an ion-imaging detector and tunable synchrotron radiation in the 18.0-37.

Stereoselectivity in Autoionization Reactions of Hydrogenated Molecules by Metastable Noble Gas Atoms: The Role of Electronic Couplings.

Focus in the present paper is on the analysis of total and partial ionization cross sections, measured in absolute value as a function of the collision energy, representative of the probability of ionic product formation in selected electronic states in Ne*-H2 O, H2 S, and NH3 collisions. In order to characterize the imaginary part of the optical potential, related to electronic couplings, we generalize a methodology to obtain direct information on the opacity function of these reactions. Such a methodology has been recently exploited to test the real part of the optical potential (S.

Measurements of Ionization Cross Sections by Molecular Beam Experiments: Information Content on the Imaginary Part of the Optical Potential.

In this work, we present and analyze in detail new and recent ionization cross section and mass spectrum determinations, collected in the case of He*, Ne*-H2O, -H2S, and -NH3 ionizing collisions. These sets of data, obtained under the same experimental conditions, are relevant to identify differences in the autoionization stereodynamics of the three hydrogenated molecules and on the selective role of the imaginary part of the optical potential. We demonstrate that in these autoionization processes hydrogen and halogen bonds are competing because they are controlling both real and imaginary components of the optical potential that drives the complete reaction dynamics.

Stereodynamics in the Collisional Autoionization of Water, Ammonia, and Hydrogen Sulfide with Metastable Rare Gas Atoms: Competition Between Intermolecular Halogen and Hydrogen Bonds.

Recent experiments on the title subject, performed with a high-resolution crossed-beam apparatus, have provided the total ionization cross sections as a function of the collision energy between noble gas atoms, electronically excited in their metastable states (Ng*), and H2 O, H2 S, and NH3 reagents, as well as the emitted electron energy spectra. This paper presents a rationalization of all the experimental findings in a unifying picture to cast light on the basic chemical properties of Ng* under conditions of great relevance both from a fundamental and from an applied point of view. The importance of this investigation is that it isolates the selective role of the intermolecular halogen and hydrogen bonds, to assess their anisotropic effects on the stereodynamics of the promoted ionization reactions, and to model energy transfer and reactivity in systems of applied interest, such as planetary atmospheres, plasmas, lasers, and flames.

Penning ionization electron spectroscopy of hydrogen sulfide by metastable helium and neon atoms.

The dynamics of the Penning ionization of hydrogen sulfide molecules by collision with helium and metastable neon atoms, occurring in the thermal energy range, has been studied by analyzing the energy spectra of the emitted electrons obtained in our laboratory in a crossed beam experiment. These spectra are compared with the photoelectron spectra measured by using He(I) and Ne(I) photons under the same experimental conditions. In this way we obtained the negative energy shifts for the formation of H2S(+) ions in the first three accessible electronic states by He*(2(3,1)S1,0) and Ne*((3)P2,0) Penning ionization collisions: the 2b1 (X̃(2)B1) fundamental one, the first 5a1 (Ã(2)A1), and the second 2b2 (B̃(2)B2) excited states, respectively.

The stereodynamics of the Penning ionization of water by metastable neon atoms.

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.

Dissociative double photoionization of benzene molecules in the 26-33 eV energy range.

A time-of-flight mass spectrometer with a position sensitive ion detector was used to study the dissociative double ionization of benzene by UV synchrotron radiation. The threshold energy for the main dissociative processes, leading to CH(3)(+) + C(5)H(3)(+), C(2)H(3)(+) + C(4)H(3)(+) and C(2)H(2)(+) + C(4)H(4)(+) ion pairs were characterized by exploiting a photoelectron-photoion-photoion-coincidence technique, giving 27.8 ± 0.

Beyond the Lennard-Jones model: a simple and accurate potential function probed by high resolution scattering data useful for molecular dynamics simulations.

Scattering data, measured for rare gas-rare gas systems under high angular and energy resolution conditions, have been used to probe the reliability of a recently proposed interaction potential function, which involves only one additional parameter with respect to the venerable Lennard-Jones (LJ) model and is hence called Improved Lennard-Jones (ILJ). The ILJ potential eliminates most of the inadequacies at short- and long-range of the LJ model. Further reliability tests have been performed by comparing calculated vibrational spacings with experimental values and calculated interaction energies at short-range with those obtained from the inversion of gaseous transport properties.

The intermolecular potential in NO-N2 and (NO-N2)+ systems: implications for the neutralization of ionic molecular aggregates.

The characterization of the non covalent interaction potential, responsible for the intermolecular bond in NO-N(2) and (NO-N(2))(+) molecular aggregates, has been achieved by coupling the predictions of a semiempirical method with the results of a scattering experiment and ab initio calculations. The potential wells for the most stable configurations of the neutral and ionic state, having approximatively a T shape in both cases, fall in the same intermolecular distance range. In addition, in the ionic state, the charge is completely localized on the NO partner.

New insights on the stereodynamics of ethylene adsorption on an oxygen-precovered silver surface.

The control of spatial orientation of molecules has a great influence on the stereodynamics of elementary processes occurring both in homogeneous and heterogeneous phases. Nonpolar molecules have so far escaped direct experimental investigations because of their poor sensitivity to several external constraints. Recently, it has been shown that the collisional alignment produced in supersonic expansions coupled with molecular-beam velocity selection can help solve such problems.