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. Important help to the solution of such a problem has been provided by the phenomenological method which adopts semi-empirical and empirical formulas to represent the basic features of the leading interaction components. Such formulas are defined in terms of a few parameters directly or indirectly related to the fundamental physical properties of the interacting partners. In this way, the basic features of the precursor state controlling its stability and its dynamical evolution have been defined in an internally consistent way for several elementary processes, having apparently different natures. Particular attention has been paid to the chemi-ionization reactions: they are treated as prototype oxidation processes for which all electronic rearrangements affecting stability and evolution of the precursor state, coincident with the reaction transition state, have been characterized in great detail. The obtained information appears to be in the perspective of general interest for many other elementary processes, difficult to investigate in the same detail since many other effects mask their basic features.

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 ClNO2+. 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. ClNO molecules crossing the photon beam at right angles in the scattering region are generated by effusive expansion and randomly oriented. The threshold energy for the double ionization of ClNO (30.1 ± 0.1 eV) and six dissociation channels producing NO+/Cl+, N+/Cl+, N+/O+, O+/Cl+, ClN+/O+, NO+/Cl2+ ion pairs, with their relative abundance and threshold energies, have been measured.

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. They are characterized by pronounced electronic rearrangements that take place within the collisional complex (X···M)* formed by approaching reagents, as shown by the following scheme, where M is an atomic or molecular target: X* + M → (X···M)* → [(X+···M) ↔ (X···M+)]e- →via⁡e-⁡CT (X···M)+ + e- → final ions.Despite their important role in fundamental and applied research, combustion, plasmas, and astrochemistry, a unifying description of these basic processes is still lacking. This Account describes a new general theoretical methodology that demonstrates, for the first time, that chemi-ionization reactions are prototypes of gas phase oxidation processes occurring via two different microscopic mechanisms whose relative importance varies with collision energy, Ec, and separation distance, R. These mechanisms are illustrated for simple collisions involving Ne*(3P2,0) and noble gases (Ng). In thermal and hyperthermal collisions probing interactions at intermediate and short R, the transition state [(Ne···Ng)+]e- is a molecular species described as a molecular ion core with an orbiting Rydberg electron in which the neon reagent behaves as a halogen atom (i.e., F) with high electron affinity promoting chemical oxidation. Conversely, subthermal collisions favor a different reaction mechanism: Ng chemi-ionization proceeds through another transition state [Ne*······Ng], a weakly bound diatomic-lengthened complex where Ne* reagent, behaving as a Na atom, loses its metastability and stimulates an electron ejection from M by a concerted emission-absorption of a "virtual" photon. This is a physical radiative mechanism promoting an effective photoionization. In the thermal regime of Ec, there is a competition between these two mechanisms. The proposed method overcomes previous approaches for the following reasons: (1) it is consistent with all assumptions invoked in previous theoretical descriptions dating back to 1970; (2) it provides a simple and general description able to reproduce the main experimental results from our and other laboratories during last 40 years; (3) it demonstrates that the two "exchange" and "radiative" mechanisms are simultaneously present with relative weights that change with Ec (this viewpoint highlights the fact that the "canonical" chemical oxidation process, dominant at high Ec, changes its nature in the subthermal regime to a direct photoionization process; therefore, it clarifies differences between the cold chemistry of terrestrial and interstellar environments and the energetic one of combustion and flames); (4) the proposed method explicitly accounts for the influence of the degree of valence orbital alignment on the selective role of each reaction channel as a function of Ec and also permits a description of the collision complex, a rotating adduct, in terms of different Hund's cases of angular momentum couplings that are specific for each reaction channel; (5) finally, the method can be extended to reaction mechanisms of redox, acid-base, and other important condensed phase reactions.

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 3PJ 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. Two basic reaction mechanisms have been identified: (i) at low collision energies, a weakly bounded transition state is formed which spontaneously ionizes through a radiative physical mechanism (photoionization); (ii) in the hyperthermal regime, an elementary oxidation process occurs. In this paper, the selectivity of the electronic rearrangements triggering the two mechanisms has been related to the angular momentum couplings by Hund's cases, casting further light on fundamental aspects of the reaction stereodynamics of general interest. The obtained results allow peculiar characteristics and differences of the terrestrial oxidizing chemistry compared to that of astrochemical environments to be highlighted.

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*(3P2,0) 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. The present paper provides the first step for the extension of the method to cases involving molecules of increasing complexity, whose chemi-ionization reactions are of relevance in several fields of basic and applied researches. The focus is here on the reactions of Ne* with simple inorganic molecules as Cl2 and NH3, and the application of the method discloses relevant features of the reaction microscopic evolution. In particular, this study shows that the balance of two fundamental reaction mechanisms depends not only on the collision energy and on the relative orientation of reagents but also on the orbital angular momentum of each collision complex. The additional insights so emphasized are of general relevance to assess in detail the stereodynamics of many other elementary processes.

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*(3P2,0) and Kr(1S0) and Xe(1S0), 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. The obtained results are important not only to compact previous theoretical schemes of autoionization reactions in a unified representation but also to cast light on the role of electronic rearrangements within the transition state of many other types of chemical processes that are more difficult to characterize.

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 18.0-37.0 eV energy range, permits us (i) to observe six double ionization fragmentation channels, their relative yields being accounted for about two-thirds by the couple (C2H4+, CH2O+) and one-fifth by (C2H3+, CH3O+); (ii) to measure thresholds for their openings as a function of photon energy; and (iii) to unravel a pronounced bimodality for a kinetic-energy-released distribution, fingerprint of competitive non-adiabatic mechanisms.

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. Falcinelli et al., Chem. Eur. J., 2016, 22, 764-771). Depending on the balance of noncovalent contributions, the real part controls the approach of neutral reactants, the removal of ionic products, and the structure of the transition state. Strength, range, and stereoselectivity of electronic couplings, triggering these and many other reactions, are directly obtained from the present investigation.

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.

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. In particular, we found that both components critically depend on the angular and radial approach between the reagent partners in determining the collision dynamics.

The stereo-dynamics of collisional autoionization of ammonia by helium and neon metastable excited atoms through molecular beam experiments.

A combined analysis of both new (energy spectra of emitted electrons) and previously published (ionization cross sections) experimental data, measured under the same conditions and concerning electronically excited lighter noble gas -NH3 collisional autoionization processes, is carried out. Such an analysis, performed by exploiting a formulation of the full potential energy surface both in the real and imaginary parts, provides direct information on energetics, structure, and lifetime of the intermediate collision complex over all the configuration space. The marked anisotropy in the attraction of the real part, driving the approach of reagents, and the selective role of the imaginary component, associated to the charge transfer coupling between entrance and exit channels, suggests that reactive events occur almost exclusively in the molecular hemisphere containing the nitrogen lone pair. Crucial details on the stereo-dynamics of elementary collisional autoionization processes are then obtained, in which the open shell nature of the disclosed ionic core of metastable atom plays a crucial role. The same analysis also suggests that the strength of the attraction and the anisotropy of the interaction increases regularly along the series Ne*((3)P), He*((3)S), He*((1)S)-NH3. These findings can be ascribed to the strong rise of the metastable atom electronic polarizability (deformability) along the series. The obtained results can stimulate state of the art ab initio calculations focused on specific features of the transition state (energetics, structure, lifetime, etc.) which can be crucial for a further improvement of the adopted treatment and to better understand the nature of the leading interaction components which are the same responsible for the formation of the intermolecular halogen and hydrogen bond.

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 recorded energy shifts indicate that in the case of He* and Ne*-H2S the autoionization dynamics depends on the features of the collision complex and is mainly driven by an effective global attraction that comes from a balance among several non covalent intermolecular interaction components. This suggests that the Penning ionization should take place, in a specific range of intermolecular distances, as we have already observed in the case of Penning ionization of water molecules [Brunetti, B. G.; Candori, P.; Falcinelli, S.; Pirani, F.; Vecchiocattivi, F. J. Chem. Phys. 2013, 139, 164305-1-164305-8].

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. 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 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*(3P2,0)-HX (X = Cl, Br) are presented in a comparative way as a function of the collision energy between 0.02-0.5 eV. New mass spectrometric data on Ne*-HBr chemi-ionization are discussed and analyzed with already published data on Ne*-HCl, highlighting similarities and differences of the collisional stereodynamics of the two systems. Basic features of the interaction potentials, driving reactive collisions, suggest that reaction channels, leading to the formation of parent HX+ ions in the ground and excited electronic state and to the formation of associated NeHX+ ions as well as of NeH+ proton transfer species, are selectively opened within angular cones exhibiting different orientation and acceptance.

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 ± 0.1, 29.5 ± 0.1, and 30.2 ± 0.1 eV, respectively. The first reaction also proceeds via the formation of a metastable C(6)H(6)(2+) dication. The translational kinetic energy of the ionic products was evaluated by measuring the position of ions arriving to the detector. Theoretical calculations of the energy and structure of dissociation product ions were performed to provide further information on the dynamics of the charge separation reactions following the photoionization event.

Selectivity of weak intermolecular forces and precursor state of elementary oxidation reactions, a new insight on Ne* + N2 chemiionization.

This paper reports on the collision dynamics of N2 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. The present analysis casts light on basic electronic rearrangements of such prototype oxidation reaction which are expected to be of fundamental interest for many other reactions involving open shell atoms and free radicals.

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*(3P2,0) noble gas atom chemi-ionizations as prototype oxidation processes. We include the selective role of atomic alignment and of the electron transfer mechanism. The state-to-state reaction probability is evaluated and a unifying description of the main experimental findings is obtained. Further, we reproduce the results of recent and advanced molecular beam experiments with a state selected Ne* beam.The selective role of electronic rearrangements within the transition state, quantified through the use of suitable operative relations, could cast light on many other chemical processes more difficult to characterize.

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*(3P2, 0) 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. Their mutual orientation with respect to the intermolecular axis controls the characteristics of the intermolecular potential, which drives the collision dynamics and the reaction probability. The investigation of ionization processes of water, the prototype of hydrogenated molecules, suggested that the ground state of water ion is produced when Ne* approaches H2O perpendicularly to its plane. Conversely, collisions addressed toward the lone pair, aligned along the water C2v symmetry axis, generates electronically excited water ions. However, obtained results refer to a statistical/random orientation of the open shell ionic core of Ne*. Recently, the attention focused on the ionization of Kr or Xe by Ne*, for which we have been able to characterize the dependence on the collision energy of the branching ratio between probabilities of spin orbit resolved elementary processes. The combined analysis of measured PIES spectra suggested the occurrence of contributions from four different reaction channels, assigned to two distinct spin-orbit states of the Ne*(3P2, 0) reagent and two different spin-orbit states of the ionic M+(2P3/2, 1/2) products (M = Kr, Xe). The obtained results emphasized the reactivity change of 3P0 atoms with respect to 3P2, in producing ions in 2P3/2 and 2P1/2 sublevels, as a function of the collision energy. These findings have been assumed to arise from a critical balance of adiabatic and non-adiabatic effects that control formation and electronic rearrangement of the collision complex, respectively. From these results we are able to characterize for the first time, according to our knowledge, the state to state reaction probability for the ionization of Kr and Xe by Ne* in both 3P2 and 3P0 sublevels.