Revisiting Numerical Solutions of Weakly Bound Noble Gases' Vibrational Energy Levels Modeled by the Improved Lennard- Jones Potential.

We revisit the numerical solutions of vibrational eigenstates of weakly bound homonuclear and heteronuclear noble gas pairs by applying a Fortran program based on the Numerov method. The harmonic, Lennard-Jones (LJ), and Improved Lennard- Jones (ILJ) potential models have been implemented to represent the potential energy curves (PECs). The obtained vibrational energies spectrum was tested on the experimental data and accurate ab initio calculations at CCSD(T)/CBS level. The vibrational eigenvalues and eigenfunctions can be reproduced accurately within the ILJ potential model. Moreover, considering from the calculated lifetime of van der Waals (vdW) complexes, the implementation of ILJ rather than standard LJ potential model has a significant impact on the systems dynamics by providing more representative atomic trajectories when the function is incorporated in force fields for molecular dynamics (MD) simulations. Overall, the ILJ function is the best suited potential model for the representation of vibrational motions and the determination of vibrational energy levels of weakly bound systems, both at equilibrium and non-equilibrium conditions.

Vibrational energy relaxation in shock-heated CO/N2/Ar mixtures.

Experimental and numerical studies were performed on the vibrational energy relaxation in shock-heated CO/N2/Ar mixtures. A laser absorption technique was applied to the time-dependent rovibrational temperature time-history measurements. The vibrational relaxation data of reflected-shock-heated CO were summarized at 1720-3230 K. In shock-tube experiments, the rotational temperature of CO quickly reached equilibrium, whereas a relaxation process was found in the time-dependent vibrational temperature. For the mixture with 1.0% CO and 10.0% N2, the vibrational excitation caused a decrease in the macroscopic thermodynamic temperature of the test gas. In the simulations, the state-to-state (StS) approach was employed, where the vibrational energy levels of CO and N2 are treated as pseudo-species. The vibrational state-specific inelastic rate coefficients of N2-Ar collisions were calculated using the mixed quantum-classical method based on a newly developed three-dimensional potential energy surface. The StS predictions agreed well with the measurements, whereas deviations were found between the Schwartz-Slawsky-Herzfeld formula predictions and the measurements. The Millikan-White vibrational relaxation data of the N2-Ar system were found to have the most significant impact on the model predictions via sensitivity analysis. The vibrational relaxation data of the N2-Ar system were then modified according to the experimental data and StS results, providing an indirect way to optimize the vibrational relaxation data of a specific system. Moreover, the vibrational distribution functions of CO and N2 and the effects of the vibration-vibration-translation energy transfer path on the thermal nonequilibrium behaviors were highlighted.

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.

Improved Quantum-Classical Treatment of N2-N2 Inelastic Collisions: Effect of the Potentials and Complete Rate Coefficient Data Sets.

In this study, complete (i.e., including all vibrational quantum numbers in an N2 vibrational ladder) data sets of vibration-to-vibration and vibration-to-translation rate coefficients for N2-N2 collisions are explicitly computed along with transport properties (shear and bulk viscosity, thermal conductivity, and self-diffusion) in the temperature range 100-9000 K. To reach this goal, we improved a mixed quantum-classical (MQC) dynamics approach by lifting the constraint of a Morse treatment of the vibrational wave function and intramolecular potential and permitting the use of more realistic and flexible representations. The new formulation has also allowed us to separately analyze the role of intra- and intermolecular potentials on the calculated rates and properties. Ab initio intramolecular potentials are indispensable for highly excited vibrational states, though the Morse potential still gives reasonable values up to v = 20. An accurate description of the long-range interaction and the van der Waals well is a requisite for the correct reproduction of qualitative and quantitative rate coefficients, particularly at low temperatures, making physically meaningful analytical representations still the best choice compared to currently available ab initio potential energy surfaces. These settings were used to directly compute the MQC rates corresponding to a large number of initial vibrational quantum numbers, and the missing intermediate values were predicted using a machine learning technique (i.e., the Gaussian process regression approach). The obtained values are reliable in the wide temperature range employed and are therefore valuable data for many communities dealing with nonlocal thermal equilibrium conditions in different environments.

The Sticking of N2 on W(100) Surface: An Improvement in the Description of the Adsorption Dynamics Further Reconciling Theory and Experiment.

The adsorption of nitrogen molecules on a (100) tungsten surface has been studied using a new potential energy surface in which long-range interactions are suitably characterized and represented by the Improved Lennard-Jones function. The new potential energy surface is used to carry out molecular dynamics simulations by adopting a semiclassical collisional method that explicitly includes the interaction with the surface phonons. The results of the sticking probability, evaluated as a function of the collision energy, are in good agreement with those obtained in the experiments and improve the already good comparison recently obtained with calculations performed using interactions from the Density Functional Theory method and corrected for long-range van der Waals contributions. The dependence of trapping probability on the surface temperature for a well-defined collision energy has also been investigated.

Attachment of Hydrogen Molecules to Atomic Ions (Na+ , Cl- ): Examination of an Adiabatic Separation of the H2 Rotational Motion.

Interactions between molecular hydrogen and ions are of interest in cluster science, astrochemistry and hydrogen storage. In dynamical simulations, H2 molecules are usually modelled as point particles, an approximation that can fail for anisotropic interactions. Here, we apply an adiabatic separation of the H2 rotational motion to build effective pseudoatom-ion potentials and in turn study the properties of (H2 )n Na+ /Cl- clusters. These interaction potentials are based on high-level ab initio calculations and Improved Lennard-Jones parametrizations, while the subsequent dynamics has been performed by quantum Monte Carlo calculations. By comparisons with simulations explicitly describing the molecular rotations, it is concluded that the present adiabatic model is very adequate. Interestingly, we find differences in the cluster stabilities and coordination shells depending on the spin isomer considered (para- or ortho-H2 ), especially for the anionic clusters.

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.

Correction: Helium nanodroplets as an efficient tool to investigate hydrogen attachment to alkali cations.

Correction for 'Helium nanodroplets as an efficient tool to investigate hydrogen attachment to alkali cations' by Siegfried Kollotzek et al., Phys. Chem. Chem. Phys., 2023, 25, 462-470, https://doi.org/10.1039/D2CP03841B.

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.

Electronic and dynamical properties of non-covalent diatomic aggregates formed by He with neutral and ionic Li and Be.

CONTEXT AND RESULTS: This work aims to study the influence of the absence and presence of permanent charges on the electronic and dynamical properties of the non-covalent bound diatomic systems involving He and Li, Be as neutral and ionic partners. The charge displacement results suggest that in the formation of HeLi[Formula: see text], HeBe[Formula: see text], and HeBe[Formula: see text], the neutral He atom undergoes, in the electric field of the ion, a pronounced electronic polarization, and the natural bond order theoretical approach indicates that in the formation of the molecular orbital He acts as a weak electron donor. The energy decomposition analysis provides the dispersion and induction components as the attractive leading terms controlling the stability of all systems, confirming that the formed bond substantially maintains a non-covalent nature which is also supported by the Quantum Theory of Atoms in Molecules (QTAIM) analysis. Finally, it was found that the HeLi and HeBe neutral systems are unstable under any condition, HeLi[Formula: see text] and HeBe[Formula: see text] ionic systems are stable below 317K and 138K, respectively, while the HeBe[Formula: see text] system becomes unstable only after 3045K. COMPUTATIONAL AND THEORETICAL TECHNIQUES: The potential energy curves and interactions in all systems were studied theoretically based on coupled-cluster singles and doubles method with perturbative inclusion of triples CCSD(T) method with an aug-cc-pV5Z basis set. More precisely, it was determined the potential energy curves describing the stability of the HeLi, HeLi[Formula: see text], HeBe, HeBe[Formula: see text], and HeBe[Formula: see text] systems, the charge displacement within the formed adducts, the decomposition of their total interaction energy, the topological analysis of their bonds, their rovibrational energies, their spectroscopic constants and lifetimes.

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.

The van der Waals interactions in systems involving superheavy elements: the case of oganesson (Z = 118).

This work presents a study involving dimers composed of He, Ne, Ar, Kr, Xe, Rn, and Og noble gases with oganesson, a super-heavy closed-shell element (Z = 118). He-Og, Ne-Og, Ar-Og, Kr-Og, Xe-Og, Rn-Og, and Og-Og ground state electronic potential energy curves were calculated based on the 4-component (4c) Dirac-Coulomb Hamiltonian and were counterpoise corrected. For the 4c calculations, the electron correlation was taken into account using the same methodology (MP2-srLDA) and basis set quality (Dyall's acv3z and Dunning's aug-cc-PVTZ). All calculations included quantum electrodynamics effects at the Gaunt interaction level. For all the aforementioned dimers the vibration energies, spectroscopic constants (ωe, ωexe, ωeye, αe, and γe), and lifetime as a function of the temperature (which ranged from 200 to 500 K) were also calculated. The obtained results suggest that the inclusion of quantum electrodynamics effects reduces the value of the dissociation energy of all hetero-nuclear molecules with a percentage contribution ranging from 0.48% (for the He-Og dimer) to 9.63% (for the Rn-Og dimer). The lifetime calculations indicate that the Og-He dimer is close to the edge of instability and that Ng-Og dimers are relatively less stable when the Gaunt correction is considered. Exploiting scaling laws that adopt the polarizability of involved partners as scaling factors, it has also been demonstrated that in such systems the interaction is of van der Waals nature (size repulsion plus dispersion attraction) and this permitted an estimation of dissociation energy and equilibrium distance in the Og-Og dimer. This further information has been exploited to evaluate the rovibrational levels in this symmetric dimer and to cast light on the macroscopic properties of condensed phases concerning the complete noble gas family, emphasizing some anomalies of Og.

Helium nanodroplets as an efficient tool to investigate hydrogen attachment to alkali cations.

We report a novel method to reversibly attach and detach hydrogen molecules to positively charged sodium clusters formed inside a helium nanodroplet host matrix. It is based on the controlled production of multiply charged helium droplets which, after picking up sodium atoms and exposure to H2 vapor, lead to the formation of Nam+(H2)n clusters, whose population was accurately measured using a time-of-flight mass spectrometer. The mass spectra reveal particularly favorable Na+(H2)n and Na2+(H2)n clusters for specific "magic" numbers of attached hydrogen molecules. The energies and structures of these clusters have been investigated by means of quantum-mechanical calculations employing analytical interaction potentials based on ab initio electronic structure calculations. A good agreement is found between the experimental and the theoretical magic numbers.

A Detailed Study of Electronic and Dynamic Properties of Noble Gas-Oxygen Molecule Adducts.

In this work, the binding features of adducts formed by a noble gas (Ng = He, Ne, Ar, Kr, Xe, and Rn) atom and the oxygen molecule (O2) in its ground Σg-3, in the past target of several experimental studies, have been characterized under different theoretical points of view to clarify fundamental aspects of the intermolecular bond. For the most stable configuration of all Ng-O2 systems, binding energy has been calculated at the theory's CCSD(T)/aug-cc-pVTZ level and compared with the experimental findings. Rovibrational energies, spectroscopic constants, and lifetime as a function of temperature were also evaluated by adopting properly formulated potential energy curves. The nature of the interaction involved was deeply investigated using charge displacement analysis, symmetry-adapted perturbation theory (SAPT), and natural bond orbital (NBO) methods. In all adducts, it was found that the charge transfer plays a minor role, although O2 is an open shell species exhibiting a positive electron affinity. Obtained results also indicate that the dispersion attraction contribution is the main responsible for the complex stability.

Scattering of N2 Molecules from Silica Surfaces: Effect of Polymorph and Surface Temperature.

The inelastic scattering of N2 molecules from silica surfaces, taken at 100 K, has been investigated by adopting a semiclassical collision model in conjunction with the appropriate treatment of the long-range interaction forces. Such forces promote the formation of the precursor state that controls all basic elementary processes occurring at the gas-surface interphase. The probabilities for the different elementary surface processes triggered by quartz are determined and compared with those recently obtained for another silica polymorph (cristobalite). In addition, the final roto-vibrational distributions of N2 molecules undergoing inelastic scattering have been characterized. N2 molecules, impinging on both considered surfaces in low-medium vibrational states, preserve the initial vibrational state, while those inelastically scattered are rotationally excited and translationally colder. The surface temperature effect, investigated by raising the temperature itself from 100 K up to 1000 K, emerges more sharply for the cristobalite polymorph, mainly for the molecules impinging in the ground roto-vibrational state and with low collision energies.

Fragmentation of interstellar methanol by collisions with He˙+: an experimental and computational study.

Methanol is a key species in astrochemistry as its presence and reactivity provides a primary route to the synthesis of more complex interstellar organic molecules (iCOMs) that may eventually be incorporated in newly formed planetary systems. In the interstellar medium, methanol is formed by hydrogenation of CO ices on grains, and its fate upon collisions with interstellar ions should be accounted for to correctly model iCOM abundances in objects at various stages of stellar evolution. The absolute cross sections (CSs) and branching ratios (BRs) for the collisions of He˙+ ions with CH3OH are measured, as a function of the collision energy, using a Guided Ion Beam Mass Spectrometer (GIB-MS). Insights into the dissociative electron (charge) exchange mechanism have been obtained by computing the entrance and exit multidimensional Potential Energy Surfaces (PESs) and by modelling the non-adiabatic transitions using an improved Landau-Zener-Stückelberg approach. Notably, the dynamical treatment reproducing the experimental findings includes a strong orientation effect of the system formed by the small He˙+ ion and the highly polar CH3OH molecule, in the electric field gradient associated to the strongly anisotropic intermolecular interaction. This is a stereodynamical effect that plays a fundamental role in collision events occurring under a variety of conditions, with kinetic energy confined within intervals ranging from the sub-thermal to the hyper-thermal regime.

Multilayer Graphtriyne Membranes for Separation and Storage of CO2: Molecular Dynamics Simulations of Post-Combustion Model Mixtures.

The ability to remove carbon dioxide from gaseous mixtures is a necessary step toward the reduction of greenhouse gas emissions. As a contribution to this field of research, we performed a molecular dynamics study assessing the separation and adsorption properties of multi-layered graphtriyne membranes on gaseous mixtures of CO2, N2, and H2O. These mixtures closely resemble post-combustion gaseous products and are, therefore, suitable prototypes with which to model possible technological applications in the field of CO2 removal methodologies. The molecular dynamics simulations rely on a fairly accurate description of involved force fields, providing reliable predictions of selectivity and adsorption coefficients. The characterization of the interplay between molecules and membrane structure also permitted us to elucidate the adsorption and crossing processes at an atomistic level of detail. The work is intended as a continuation and a strong enhancement of the modeling research and characterization of such materials as molecular sieves for CO2 storage and removal.

Molecular hydrogen isotope separation by a graphdiyne membrane: a quantum-mechanical study.

Graphdiyne (GDY) has emerged as a very promising two-dimensional (2D) membrane for gas separation technologies. One of the most challenging goals is the separation of deuterium (D2) and tritium (T2) from a mixture with the most abundant hydrogen isotope, H2, an achievement that would be of great value for a number of industrial and scientific applications. In this work we study the separation of hydrogen isotopes in their transport through a GDY membrane due to mass-dependent quantum effects that are enhanced by the confinement provided by its intrinsic sub-nanometric pores. A reliable improved Lennard-Jones force field, optimized on accurate ab initio calculations, has been built to describe the molecule-membrane interaction, where the molecule is treated as a pseudoatom. The quantum dynamics of the molecules impacting on the membrane along a complete set of incidence directions have been rigorously addressed by means of wave packet calculations in the 3D space, which have allowed us to obtain transmission probabilities and, in turn, permeances, as the thermal average of the molecular flux per unit pressure. The effect of the different incidence directions on the probabilities is analyzed in detail and it is concluded that restricting the simulations to a perpendicular incidence leads to reasonable results. Moreover, it is found that a simple 1D model-using a zero-point energy-corrected interaction potential-provides an excellent agreement with the 3D probailities for perpendicular incidence conditions. Finally, D2/H2 and T2/H2 selectivities are found to reach maximum values of about 6 and 21 at ≈50 and 45 K, respectively, a feature due to a balance between zero-point energy and tunneling effects in the transport dynamics. Permeances at these temperatures are below recommended values for practical applications, however, at slightly higher temperatures (77 K) they become acceptable while the selectivities preserve promising values, particularly for the separation of tritium.

Intermolecular Forces: From Atoms and Molecules to Nanostructures.

Intermolecular forces, determined by the critical balance of interacting components having physical and chemical natures, control most of the static and dynamic properties of matter such as their existence in solid, liquid and gaseous phases, with their relative stability, and their chemical reactivity [...].

Unsaturated Dinitriles Formation Routes in Extraterrestrial Environments: A Combined Experimental and Theoretical Investigation of the Reaction between Cyano Radicals and Cyanoethene (C2H3CN).

The reaction between cyano radicals (CN, X2Σ+) and cyanoethene (C2H3CN) has been investigated by a combined approach coupling crossed molecular beam (CMB) experiments with mass spectrometric detection and time-of-flight analysis at a collision energy of 44.6 kJ mol-1 and electronic structure calculations to determine the relevant potential energy surface. The experimental results can be interpreted by assuming the occurrence of a dominant reaction pathway leading to the two but-2-enedinitrile (1,2-dicyanothene) isomers (E- and Z-NC-CH═CH-CN) in a H-displacement channel and, to a much minor extent, to 1,1-dicyanoethene, CH2C(CN)2. In order to derive the product branching ratios under the conditions of the CMB experiments and at colder temperatures, including those relevant to Titan and to cold interstellar clouds, we have carried out RRKM statistical calculations using the relevant potential energy surface of the investigated reaction. We have also estimated the rate coefficient at very low temperatures by employing a semiempirical method for the treatment of long-range interactions. The reaction has been found to be barrierless and fast also under the low temperature conditions of cold interstellar clouds and the atmosphere of Titan. Astrophysical implications and comparison with literature data are also presented. On the basis of the present work, 1,2-dicyanothene and 1,1-dicyanothene are excellent candidates for the search of dinitriles in the interstellar medium.