The dawn of hydrogen and halogen bonds and their crucial role in collisional processes probing long-range intermolecular interactions.

This perspective review focuses on the results of an internally consistent study developed in the Perugia laboratory, centered on the fundamental interaction components that, at large intermolecular distances, determine the formation of weak intermolecular hydrogen (HB) and halogen (XB) bonds. This investigation exploits old and novel molecular beam scattering experiments involving several gaseous prototypical systems. In particular, we focus on the kinetic energy dependence of the total (elastic + inelastic) integral cross-sections. Of particular interest is the measure of quantum interference patterns in the energy dependence of cross-sections of targeted systems and their shift compared to that of known reference systems. We interpreted these findings as interaction energy stabilization components, such as charge transfer, σ-hole, and polar flattening, that emerge at intermediate separation distance ranges and selectively manifest for specific geometries of collision complexes. Another significant observable we discuss is the absolute value of the cross-section and its dependence on permanent multipole moments of the collisional partners. Specifically, we show how the spontaneous orientation of rotationally cold and polar molecules, due to the electric field gradient associated with the interaction between permanent multipole moments, can significantly modify the magnitude of the total cross-section, even at high values of the impact parameter. We are confident that the present results can help extend the force field formulation to various interacting systems and carry out molecular dynamics simulations under conditions of application interest.

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.

Electronic state influence on selective bond breaking of core-excited nitrosyl chloride (ClNO).

The potential for selective bond breaking of a small molecule was investigated with electron spectroscopy and electron-ion coincidence experiments on ClNO. The electron spectra were measured upon direct valence photoionization and resonant core excitation at the N 1s- and O 1s-edges, followed by the emission of resonant-Auger (RA) electrons. The RA spectra were analyzed with particular emphasis on the assignment of the participator and spectator states. The states are of special relevance for investigating how distinct electronic configurations influence selective bond breaking. The electron-ion coincidence measurements provided branching fractions of the produced ion fragments as a function of electron binding energy. They explicitly demonstrate how the final electronic states created after photoionization and RA decay influence fragmentation. In particular, we observed a significantly different branching fraction for spectator states compared with participator states. In addition, it was also observed that the bonds broken for the spectator states correlate with the antibonding nature of the spectator-electron orbital.

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.

Molecular beam scattering experiments on noble gas-propylene oxide: Total integral cross sections and potential energy surfaces of He- and Ne-C3H6O.

The interactions of He and Ne with propylene oxide have been investigated with the molecular beam technique by measuring the total (elastic + inelastic) integral cross section as a function of collision velocity. Starting from the analysis of these experimental data, potential energy surfaces, formulated as a function of the separation distance and orientation of propylene oxide with respect to the interacting partners, have been built: The average depth of potential wells (located at intermediate separation distances) has been characterized by analyzing the observed "glory" quantum effects, and the strength of long-range attractions has been obtained from the magnitude and the velocity dependence of the smooth component of measured cross sections. The surfaces, tested and improved against new ab initio calculations of minima interaction energies at the complete basis set level of theory, are defined in the full space of relative configurations. This represents a crucial condition to provide force fields useful to carry out, in general, important molecular property simulations and to evaluate, in the present case, the spectroscopic features and the dynamical selectivity of weakly bound complexes formed by propylene oxide, a prototype chiral species, during collisions in interstellar clouds and winds, in the space and planetary atmospheres. The adopted formulation of the interaction can be readily extended to similar systems, involving heavier noble gases or diatomic molecules (H2, O2, and N2) as well as to propylene oxide dimers.

Production and Characterization of Molecular Dications: Experimental and Theoretical Efforts.

Molecular dications are doubly charged cations of importance in flames, plasma chemistry and physics and in the chemistry of the upper atmosphere of Planets. Furthermore, they are exotic species able to store a considerable amount of energy at a molecular level. This high energy content of several eV can be easily released as translational energy of the two fragment monocations generated by their Coulomb explosion. For such a reason, they were proposed as a new kind of alternative propellant. The present topic review paper reports on an overview of the main contributions made by the authors' research groups in the generation and characterization of simple molecular dications during the last 40 years of coupling experimental and theoretical efforts.

Leading Interaction Components in the Structure and Reactivity of Noble Gases Compounds.

The nature, strength, range and role of the bonds in adducts of noble gas atoms with both neutral and ionic partners have been investigated by exploiting a fine-tuned integrated phenomenological-theoretical approach. The identification of the leading interaction components in the noble gases adducts and their modeling allows the encompassing of the transitions from pure noncovalent to covalent bound aggregates and to rationalize the anomalous behavior (deviations from noncovalent type interaction) pointed out in peculiar cases. Selected adducts affected by a weak chemical bond, as those promoting the formation of the intermolecular halogen bond, are also properly rationalized. The behavior of noble gas atoms excited in their long-life metastable states, showing a strongly enhanced reactivity, has been also enclosed in the present investigation.

Insight into the halogen-bond nature of noble gas-chlorine systems by molecular beam scattering experiments, ab initio calculations and charge displacement analysis.

We have carried out molecular-beam scattering experiments and high-level ab initio investigations on the potential energy surfaces of a series of noble-gas-Cl2 adducts. This effort has permitted the construction of a simple, reliable and easily generalizable analytical model potential formulation, which is based on a few physically meaningful parameters of the interacting partners and transparently shows the origin, strength, and stereospecificity of the various interaction components. The results demonstrate quantitatively beyond doubt that the interaction between a noble-gas (Ng) atom - even He - and Cl2 in a collinear configuration is characterized by weak halogen bond (XB) formation, accompanied by charge transfer (CT) from the Ng to chlorine. This characteristic, which stabilizes the adduct, rapidly disappears on going towards the T-shaped configuration, dominated by pure van der Waals (vdW) forces. Similarly, a pure vdW interaction takes place - with no CT component in any configuration - if Cl2 is present in the lowest πg* → σu* excited state, because the change in electron density that accompanies the excitation eliminates the Cl2 polar flattening and σ hole, making the XB interaction inaccessible.

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.

Selective Emergence of the Halogen Bond in Ground and Excited States of Noble-Gas-Chlorine Systems.

Molecular-beam scattering experiments and theoretical calculations prove the nature, strength, and selectivity of the halogen bonds (XB) in the interaction of halogen molecules with the series of noble gas (Ng) atoms. The XB, accompanied by charge transfer from the Ng to the halogen, is shown to take place in, and measurably stabilize, the collinear conformation of the adducts, which thus becomes (in contrast to what happens for other Ng-molecule systems) approximately as bound as the T-shaped form. It is also shown how and why XB is inhibited when the halogen molecule is in the 3 Πu excited state. A general potential formulation fitting the experimental observables, based on few physically essential parameters, is proposed to describe the interaction accurately and is validated by ab initio computations.

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.

Chemical Characterization of Lodoicea maldivica Fruit.

In the present study, we report the attempt to characterize the chemical composition of fruit kernel of Lodoicea maldivica coco nucifera palm (commonly named as 'Coco de mer') by gas chromatographic method. The analysis was performed by HS-SPME and GC/MS techniques to determine volatile aroma, sterol, and fatty acid composition profiles in the internal and external pulp of two distinct coconuts. Although no qualitative differences in flavour composition were observed between the two analysed coconuts and the relative two pulp parts, variations in the abundance levels of the prominent compounds have been recorded. The averaged quantity of total phytosterols, resulting from the two analysed 'Coco de mer' samples, was almost constant in both kernels coconut, being 24.5 µg/g (of dry net matter) for the external, and 26.9 µg/g (of dry net matter) for the internal portion. In both coconuts, the fatty acid pattern composition was characterized by seven saturated acids ranged from C14:0 (myristic) to C20:0 (arachidic) and two monounsaturated acids, the palmitoleic (C16:1, ω7) and the oleic (C18:1, ω9). Palmitic acid (C16:0) was the predominant one with an average contribution of about 49.0%, followed by pentadecanoic 16.5%, stearic (C18:0) 11.6%, and myristic (C14:0) 9.9% acids in all two examined kernel portions.

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.

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.

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.

Reaction Dynamics of O((3)P) + Propyne: I. Primary Products, Branching Ratios, and Role of Intersystem Crossing from Crossed Molecular Beam Experiments.

We performed synergic experimental/theoretical studies on the mechanism of the O((3)P) + propyne reaction by combining crossed molecular beams experiments with mass-spectrometric detection and time-of-flight analysis at 9.2 kcal/mol collision energy (Ec) with ab initio electronic structure calculations at a high level of theory of the relevant triplet and singlet potential energy surfaces (PESs) and statistical calculations of branching ratios (BRs) taking into account intersystem crossing (ISC). In this paper (I) we report the results of the experimental investigation, while the accompanying paper (II) shows results of the theoretical investigation with comparison to experimental results. By exploiting soft electron ionization detection to suppress/mitigate the effects of the dissociative ionization of reactants, products, and background gases, product angular and velocity distributions at different charge-to-mass ratios were measured. From the laboratory data angular and translational energy distributions in the center-of-mass system were obtained for the five competing most important product channels, and product BRs were derived. The reactive interaction of O((3)P) with propyne under single collision conditions is mainly leading to the rupture of the three-carbon atom chain, with production of the radical products methylketenyl + atomic hydrogen (BR = 0.04), methyl + ketenyl (BR = 0.10), and vinyl + formyl (BR = 0.11) and the molecular products ethylidene/ethylene + carbon monoxide (BR = 0.74) and propandienal + molecular hydrogen (BR = 0.01). Because some of the products can only be formed via ISC from the entrance triplet to the low-lying singlet PES, we infer from their BRs an amount of ISC larger than 80%. This value is dramatically large when compared to the negligible ISC reported for the O((3)P) reaction with the simplest alkyne, acetylene. At the same time, it is much larger than that (∼20%) recently observed in the related reaction of the three-carbon atom alkene, O((3)P) + propene at a comparable Ec. This poses the question of how important it is to consider nonadiabatic effects and their dependence on molecular structure for this kind of combustion reactions. The prevalence of the CH3 over the H displacement channels is not explained by invoking a preference for the addition on the methyl-substituted acetylenic carbon atom, but rather it is believed to be due to the different tendencies of the two addition triplet intermediates CH3CCHO (preferentially leading to H elimination) and CH3COCH (preferentially leading to CH3 elimination) to undergo ISC to the underlying singlet PES. It is concluded that the main coproduct of the CO forming channel is singlet ethylidene ((1)CH3CH) rather than ground-state ethylene. By comparing the derived BRs with those very recently derived from kinetics studies at room temperature and 4 Torr we obtained information on how BRs vary with collision energy. The extent of ISC is estimated to remain essentially constant (∼85%) with increasing Ec from ∼1 to ∼10 kcal/mol. The present experimental results shed light on the mechanism of the title reaction at energies comparable to those involved in combustion and, when compared with the results from the statistical calculations on the ab initio coupled PESs (see accompanying paper II), lead to an in-depth understanding of the rather complex reaction mechanism of O + propyne. The overall results are expected to contribute to the development of more refined models of hydrocarbon combustion.