Noble Gas Atoms Research Articles

Stability-Order Reversal in FSiY and FYSi (Y = N and P) Molecules after the Insertion of a Noble Gas Atom.

Recent theoretical prediction and experimental identification of fluorinated noble gas cyanides and isocyanides motivate us to explore a unique novel series of neutral noble gas-inserted heavier cyanofluoride isomers, FNgYSi and FNgSiY (Ng = Kr, Xe, and Rn; Y = N and P), theoretically using quantum chemical calculations. The concerned minima and saddle point geometries have been optimized using DFT, MP2, and CCSD(T) methods. The precursor molecule FSiY is more stable than its isomer FYSi, and the stability order is found to be reversed after the insertion of a noble gas (Ng) atom into them which is in contrast to the previously reported FCN/FNC systems where the stability order in the precursors remains intact after the insertion of a Ng atom into them. The predicted FNgYSi molecules are metastable in nature as they are kinetically stable but thermodynamically unstable with respect to the global minima products (FYSi and Ng). All the calculations for the corresponding FNgSiY molecules clearly indicate that the less stable FNgSiY behaves similarly to the FNgYSi in all respects. The energetics, force constant, and spectroscopic data strongly reinforce the possibility of occurrence of these predicted FNgYSi and FNgSiY molecules which might be experimentally realized under suitable cryogenic condition(s).

Potential Energy Surfaces for Noble Gas (Ar, Kr, Xe, Rn)–Propylene Oxide Systems: Analytical Formulation and Binding

Multidimensional potential energy surfaces for heavy noble gas–propylene oxide systems are obtained by applying the phenomenological method successfully used to describe homologous systems involving He and Ne atoms. Such potential energy surfaces, where the interaction exclusively arises from the anisotropic van der Waals interaction components, are given in an analytical form. Therefore, they can be easily used as force fields to carry out molecular simulations to evaluate spectroscopic features and the dynamical selectivity of weakly bound complexes formed by propylene oxide (a prototype chiral species) with a noble gas atom (a prototype isotropic partner) by two-body collisions under a variety of conditions. Several potential energy minima are identified on the surfaces, which are confirmed and characterized by high level ab initio calculations. The next step to further generalize this methodology is its extension to systems involving propylene oxide-diatomic molecules (as H2, O2 and N2), as well as to propylene oxide dimers.

Energy Transfer in the 2 u (1 D 2) Ion-Pair State of I2 by Inelastic Collisions with Noble Gas Atoms.

We investigated the energy transfer in the 2u (1D2) ion-pair state of I2 by collision with noble gas atoms, Ar, Kr, and Xe, using an optical–optical double resonance/fluorescence detection technique. By analyzing the temporal profiles of the emission from the laser-excited 2u (1D2) state at various noble gas pressures, the quenching rate constants were determined to be (4.55 ± 0.42) × 10–10, (4.23 ± 0.11) × 10–10, and (6.83 ± 0.16) × 10–10 cm3 molecule–1 s–1 for quenching by Ar, Kr, and Xe, respectively. The 2g (1D2) ion-pair state, lying in the vicinity of the 2u (1D2) state, was identified as a destination state by collision with Ar and Kr. Collision with Xe provided a new reactive pathway forming the excimer XeI(B). The rate constants were determined to be = (9.61 ± 0.63) × 10–11 cm3 molecule–1 s–1 and = (4.87 ± 0.34) × 10–11 cm3 molecule–1 s–1 for the formation of the 2g (1D2) state by collision with Ar and Kr, respectively, and = (6.55 ± 0.19) × 10–11 cm3 molecule–1 s–1 for the formation of XeI(B). The collisional cross sections calculated from the quenching rate constants were considerably larger than the molecular size, owing to the harpoon mechanism.

Noble-gas compounds: A general procedure of bonding analysis.

This paper accounts for a general procedure of bonding analysis that is, expectedly, adequate to describe any type of interaction involving the noble-gas (Ng) atoms. Building on our recently proposed classification of the Ng-X bonds (X = binding partner) [New J. Chem. 44, 15536 (2020)], these contacts are first distinguished into three types, namely, A, B, or C, based on the topology of the electron energy density H(r) and on the shape of its plotted form. Bonds of type B or C are, then, further assigned as B-loose (Bl) or B-tight (Bt) and C-loose (Cl) or C-tight (Ct) depending on the sign that H(r) takes along the Ng-X bond path located from the topological analysis of ρ(r), particularly at around the bond critical point (BCP). Any bond of type A, Bl/Bt, or Cl/Ct is, finally, assayed in terms of contribution of covalency. This is accomplished by studying the maximum, minimum, and average value of H(r) over the volume enclosed by the low-density reduced density gradient (RDG) isosurface associated with the bond (typically, the RDG isosurface including the BCP) and the average ρ(r) over the same volume. The bond assignment is also corroborated by calculating the values of quantitative indices specifically defined for the various types of interactions (A, B, or C). The generality of our taken approach should encourage its wide application to the study of Ng compounds.

In silico capture of noble gas atoms with a light atom molecule

Noble gas atoms (Ng = He, Ne, Ar, and Kr) can be captured in silico with a light atom molecule containing only C, H, Si, O, and B atoms. Extensive density functional theory (DFT) calculations on series of peri-substituted scaffolds indicate that confined spaces (voids) capable to energy efficiently encapsulate and bind Ng atoms are accessible by design of a tripodal peri-substituted ligand, namely, [(5-Ph2B-xan-4-)3Si]H (xan = xanthene) comprising (after hydride abstraction) four Lewis acidic sites within the cationic structure [(5-Ph2B-xan-4-)3Si]+. The host (ligand system) thereby provides an adoptive environment for the guest (Ng atom) to accommodate for its particular size. Whereas considerable chemical interactions are detectable between the ligand system and the heavier Ng atoms Kr and Ar in the host guest complex [(5-Ph2B-xan-4-)3Si·Ng]+, the lighter Ng atoms Ne and He are rather tolerated by the ligand system instead of being chemically bound to it, nicely highlighting the gradual onset of (weak) chemical bonding along the series He to Kr. A variety of real-space bonding indicators (RSBIs) derived from the calculated electron and pair densities provides valuable insight to the situation of an "isolated atom in a molecule" in case of He, uncovering its size and shape, whereas minute charge rearrangements caused by polarization of the outer electron shell of the larger Ng atoms results in formation of polarized interactions for Ar and Kr with non-negligible covalent bond contributions for Kr. The present study shows that noble gas atoms can be trapped by small light-atom molecules without the forceful conditions necessary using cage structures such as fullerenes, boranes and related compounds or by using super-electrophilic sites like [B12(CN)11]- if the chelating effect of several Lewis acidic sites within one molecule is employed.

First principles molecular dynamics calculations of the mechanical properties of endofullerenes containing noble gas atoms or small molecules.

The mechanical properties of endofullerenes have been investigated by performing compression tests using finite temperature first principles molecular dynamics calculations. We considered various X@C60 systems, with X a single noble gas atom (He, Ne, Ar, Kr, or Xe), small molecules (H2O, CH4), or small helium clusters. In the absence of compression, it is observed that there is no or at best a negligible effect of X on the properties of C60. The compression simulations revealed several original findings. First, the influence of X on the stiffness of X@C60 can be quantified, although it is at most 12% for the studied cases. Next, both energy and contact force variations as a function of strain are demonstrated to depend on X. However, this is not the case for the yield strain and for the failure mechanism of the C60 shell. Finally, it is shown that the X@C60 compression could bring X to be in a high stress state. In the specific cases of H2O and CH4 molecules, a mechanism of stress assisted dissociation is observed.

Noble gas control of diamond-like content and compressive stress in carbon films by arc-mixed mode high power impulse magnetron sputtering

Conventional DC magnetron sputter deposition from a carbon target with argon as the sputtering gas is limited by a low deposition rate, and the resultant coatings have low diamond-like sp 3 content. Here we study arc-mixed mode high power impulse magnetron sputtering (HiPIMS) of carbon using He, Ne, Ar, Xe and Kr gases and show an increase in deposition rate is achieved by using noble gases heavier than argon. On the other hand, a higher sp 3 fraction is achieved by using noble gases lighter than argon. The higher deposition rate of the heavier noble gases is attributed to the higher sputtering yield and an earlier arc onset owing to their lower ionization potential . The higher sp 3 fraction achieved by lighter noble gases is attributed to stress generation by knock-on collisions at the surface of the depositing film, in the absence of stress relief created by large thermal spike volumes. When neon was used as the sputtering gas, the inert gas content was higher than for any other noble gas. Our results lead to opportunities for grading the sp 3 content with depth simply by changing the gas composition, allowing fabrication of buried conductive channels in ta-C, Metal-Insulator-Metal (MIM) (low sp 3 /high sp 3 /low sp 3 ) structures and biosensor films (high sp 3 /low sp 3 ). • Arc-mixed mode HiPIMS deposition of carbon films with He, Ne, Ar, Xe, and Kr noble gases. • The highest sp 3 fraction is achieved by He-Ne mixtures, attributed to effective momentum transfer. • The density and compressive stress in the films decrease with increasing size of noble gas atoms. • The results suggest creating buried conduction channels by changing the sputter gas composition.

Anomaly in the electron orbital g-factor: analysis of data on Ar, Ne and He

Deviations from the exact value 1, of the electron orbital g-factor are determined from the measured ratios of some states of the noble gas atoms He, Ne and Ar. The calculated values are compared with those previously found from the ratio of the Lande g-factors measured on the atoms of In, Ga and Na. The anomalies obtained from some of the rare gas atoms are, at least, one order of magnitude higher, in absolute value, than those from the one-valence-electron atoms. Configuration interactions and perturbations are considered for the atomic states analyzed and are found to be negligible. Thus, the electron’s orbital g-factor appears significantly anomalous. The implications for QED and the structure of the electron are discussed.

Does the Presence of a Bond Path Really Mean Interatomic Stabilization? The Case of the Ng@Superphane (Ng = He, Ne, Ar, and Kr) Endohedral Complexes

Using a fairly structurally flexible and, therefore, very suitable for this type of research, superphane molecule, we demonstrate that the inclusion of a noble gas atom (Ng = He, Ne, Ar, and Kr) inside it and, thus, the formation of the Ng@superphane endohedral complex, leads to its ‘swelling’. Positive values of both the binding and strain energies prove that encapsulation and in turn ‘swelling’ of the superphane molecule is energetically unfavorable and that the Ng⋯C interactions in the interior of the cage are destabilizing, i.e., repulsive. Additionally, negative Mayer Bond Orders indicate the antibonding nature of Ng⋯C contacts. This result in combination with the observed Ng⋯C bond paths shows that the presence of a bond path in the molecular graph does not necessarily prove interatomic stabilization. It is shown that the obtained conclusions do not depend on the computational methodology, i.e., the method and the basis set used. However, on the contrary, the number of bond paths may depend on the methodology. This is yet another disadvantageous finding that does not favor the treatment of bond paths on molecular graphs as indicators of chemical bonds. The Kr@superphane endohedral complex features one of the longest C–C bonds ever reported (1.753 Å).

Efficient Helium and Helium Isotopes Separation by Phosphorus Carbide P2C3 Membrane

AbstractThe problem of ever‐increasing industrial demand versus the supply shortage of helium (He) is inevitably encountered by scientists worldwide. Membrane‐based separation technology provides an economical method to alleviate the current He scarcity. In this study, using a combination of first‐principles calculations and molecular dynamics simulations, it is theoretically demonstrated that the phosphorus carbide membrane P2C3 possesses high efficiency in He separation from the natural gas (H2, N2, CO, H2O, CO2, and CH4) and other noble gas atoms (Ne and Ar). In addition, the He permeance exceeds 10–4 mol m–2 s–1 Pa–1 over a wide range of temperatures (200–500 K), which is far beyond the industrially acceptable value. Combining the zero‐point‐energy and quantum tunneling effects, the quantum analysis shows that the P2C3 membrane has great potential for 3He/4He isotope separation, thus providing a combined means for both He and 3He isotope separation. The results uncover a new solution of utilizing P2C3 nanomaterial as a novel medium for gas treatment and the findings of this study will promote experimental efforts in the future.

Excitation and Quencing of Rotational Energy Levels of the О3 Ozone Molecule by Collisions with Noble Gas Atoms (Ar and He)

Excitation and Quencing of Rotational Energy Levels of the О3 Ozone Molecule by Collisions with Noble Gas Atoms (Ar and He)

High-lying Rydberg atoms surviving intense laser fields

In this work, we have experimentally and theoretically investigated the high-lying Rydberg state excitation for noble gas atoms subject to an intense near-infrared laser field. To obtain the signal of these high-lying Rydberg atoms which are further ionized by a constant electric field $({F}_{c})$, coincident detection of the photoelectrons and photoions with well-chosen arrival times is performed. Based on a fitting to the time dependence of the coincidently measured photofragment yields with a semiempirical formula, we can extract a principal quantum number distribution (PQND) of the population of the excited states in a range closely related to the strength of ${F}_{c}$. The extracted valid PQND is in qualitative agreement with a semiclassical model calculation. Our work thus provides a method to extract the PQND and study the ultrafast high-lying Rydberg state excitation.

Self-assembling of the neutral intermediate with chemically bound argon in photoexcited van der Waals complex Ar-I2.

Photodissociation of the van der Waals complex Ar-I2 after excitation into the Rydberg states of I2 has been investigated with velocity map imaging of photofragments. Formation of the translationally hot ions of argon Ar+ with three modes in kinetic energy distribution has been revealed. The measured dependence of the kinetic energy of Ar+ on the pumping photon energy indicates the appearance of Ar+ from three channels of the photodissociation of the linear intermediate Ar+-I-I- containing chemically bound argon. These channels are (1) dissociation into Ar++ I2 -; (2) three-body dissociation into (Ar+)* + I* + I-, with (Ar+)* and I* being the 2P1/2 states of the species; and (3) two-body electron photodetachment, giving rise to Ar+ + I2 + e. Three indicated channels are similar to those established for the photodissociation of trihalide anions. This similarity confirms the conclusion on the formation of the Ar+-I-I- intermediate, which is isoelectronic to the trihalide anion Cl-I-I-. The mechanism of the Ar+-I-I- formation involves two-photon excitation of the complex Ar-I2 into the Rydberg state of I2 converted into the ion-pair state and further electron transfer from Ar to I+ of the ion-pair state. The self-assembling of the structure making the formation of the Ar+-I-I- intermediate energetically accessible is confirmed by modeling the dynamics in the excited linear complex Ar-I2. Photoexcitation of the van der Waals complexes of noble gases with halogens into the ion-pair states of halogen is supposed to be a promising approach for generating the new chemical compounds of noble gas atoms.

Molecular simulation of Rayleigh-Brillouin scattering in binary gas mixtures and extraction of the rotational relaxation numbers.

Rayleigh-Brillouin scattering (RBS) in gases has received considerable attention due to its applications in LIDAR (light detection and ranging) remote sensing and gas property measurements. In most cases, the RBS spectra in the kinetic regime are calculated based on kinetic model equations, which are difficult to be applied to complex gas mixtures. In this work, we employ two widely used molecular simulation methods, i.e., direct simulation Monte Carlo (DSMC) and molecular dynamics (MD), to calculate the spontaneous RBS spectra of binary gas mixtures. We validate these two methods by comparing the simulation results for mixtures of argon and helium with the experimental results. Then we extend the RBS calculations to gas mixtures involving polyatomic gases. The rotational relaxation numbers specific to each species pair in DSMC are determined by fitting the DSMC spectra to the MD spectra. Our results show that all the rotational relaxation numbers for air composed of N_{2} and O_{2} increase with temperature in the range of 300-750 K. We further calculate the RBS spectra for binary mixtures composed of N_{2} and one noble monatomic gas, and the simulation results show that the rotational relaxation of N_{2} is greatly affected by the mass of the noble gas atoms. This work demonstrates that RBS is a promising and alternative way to study the rotational relaxation process in gas mixtures.

Analytical approximation of cross sections of collisions of electrons with atoms of inert gases

The paper presents an analysis of data on the cross sections of elastic and inelastic collisions of electrons with noble gas atoms. The transport (diffusion) cross sec-tion, the excitation and ionization cross sections are considered. For the selected sets of experimental and theoretical data, optimal analytical formulas are found and approximation coefficients are selected for them. The obtained semi-empirical formulas allow us to reproduce the cross section values in a wide range of colli-sion energies from 0.001 to 10000 eV with an accuracy of several percent.

Optical Radiation from the Sputtered Species under Excitation of Ternary Mixtures of Noble Gases by the 6Li(n,α)3H Nuclear Reaction Products

The present paper examines the luminescence of ternary Ar-Kr-Xe and Ne-Ar-Kr mixtures of noble gases in the spectral range from 300 to 970 nm, excited by the 6Li(n,α)3H nuclear reaction products in the core of a nuclear reactor. A thin layer of lithium applied on the walls of the experimental device, stabilized in the matrix of the capillary-porous structure, serves as a source of gas excitation. During in-pile tests, conducted at the IVG.1M research reactor, thermal neutrons interact via the 6Li(n,α)3H reaction, and the emergent alpha particles with a kinetic energy of 2.05 MeV and tritium ions with a kinetic energy of 2.73 MeV excite gaseous medium. The study was carried out in a wide temperature range. The temperature dependence of the intensity of the emission of the atoms of noble gases and alkali metals, heteronuclear ionic molecules of noble gases were studied. The obtained values of the activation energy of the emission process 1.58 eV for lithium and 0.72 eV for potassium agree well with the known values of evaporation energy. Excitation of alkali metals atoms occurs consequently of the Penning process of alkali metals atoms on noble gas atoms in the 1s-states and further ion-molecular reactions.

Quantum-mechanical force balance between multipolar dispersion and Pauli repulsion in atomic van der Waals dimers

The structure and stability of atomic and molecular systems with van der Waals (vdW) bonding are often determined by the interplay between attractive dispersion interactions and repulsive interactions caused by electron confinement. Arising due to different mechanisms -- electron correlation for dispersion and the Pauli exclusion principle for exchange-repulsion -- these interactions do not appear to have a straightforward connection. In this paper, we use a coarse-grained approach for evaluating the exchange energy for two coupled quantum Drude oscillators and investigate the mutual compensation of the attractive and repulsive forces at the equilibrium distance within the multipole expansion of the Coulomb potential. This compensation yields a compact formula relating the vdW radius of an atom to its multipole polarizabilities, $R_{\rm vdW} = A_l^{\,}\, \alpha_l^{{2}/{7(l+1)}}$, where $l$ is the multipole rank and $A_l$ is a conversion factor. Such a relation is compelling because it connects an electronic property of an isolated atom (atomic polarizability) with an equilibrium distance in a dimer composed of two closed-shell atoms. We assess the accuracy of the revealed formula for noble-gas, alkaline-earth, and alkali atoms and show that the $A_l$ can be assumed to be universal constants. Besides a seamless definition of vdW radii, the proposed relation can also be used for the efficient determination of atomic multipole polarizabilities solely based on the corresponding dipole polarizability and the vdW radius. Finally, our work provides a basis for the construction of efficient and minimally-empirical interatomic potentials by combining multipolar interatomic exchange and dispersion forces on an equal footing.

Atomic Clusters: Structure, Reactivity, Bonding, and Dynamics.

Atomic clusters lie somewhere in between isolated atoms and extended solids with distinctly different reactivity patterns. They are known to be useful as catalysts facilitating several reactions of industrial importance. Various machine learning based techniques have been adopted in generating their global minimum energy structures. Bond-stretch isomerism, aromatic stabilization, Rener-Teller effect, improved superhalogen/superalkali properties, and electride characteristics are some of the hallmarks of these clusters. Different all-metal and nonmetal clusters exhibit a variety of aromatic characteristics. Some of these clusters are dynamically stable as exemplified through their fluxional behavior. Several of these cluster cavitands are found to be agents for effective confinement. The confined media cause drastic changes in bonding, reactivity, and other properties, for example, bonding between two noble gas atoms, and remarkable acceleration in the rate of a chemical reaction under confinement. They have potential to be good hydrogen storage materials and also to activate small molecules for various purposes. Many atomic clusters show exceptional opto-electronic, magnetic, and nonlinear optical properties. In this Review article, we intend to highlight all these aspects.

Measurement of a129Xe transverse relaxation rate without the influence of Rb polarization-induced magnetic gradient.

We demonstrate the measurement of the transverse spin relaxation rate of Xe without the influence of the Rb polarization-induced magnetic field gradient. The optical pumping beam and probe beam turn on and off repeatedly during the measurement to reduce the relaxation originating from the Rb polarization-induced magnetic field gradient. During the absence of the optical pumping beam, the nuclear spin of the noble gas atom does not experience the alkali-polarization-induced magnetic field gradient so that the transverse spin relaxation rate (1/T2) decreases. When the duty cycle reaches zero, the measured transverse relaxation time T2 approaches the longitudinal spin relaxation time T1. Our method helps in roughly estimating the longitudinal spin relaxation time with a single measurement of the free induction decay.

Noble Gas in a Ring.

We have designed a new type of molecule with a noble gas (Ng = Kr and Xe) atom in a six-membered ring. Their structures and stability have been studied by density functional theory and by correlated electronic structure calculations. The results showed that the six-membered ring is planar with very short Ng–O and Ng–N polar covalent bonds. The calculated energy barriers for all the unimolecular dissociation pathways are higher than 20 and 35 kcal/mol for Ng = Kr and Xe, respectively. The current study suggests that these molecules and their derivatives might be synthesized and observable at cryogenic conditions.