Rare Gas Atoms Research Articles

Atomic Rare Gas Metastable Monitoring through Nitrogen Emission in Atmospheric Pressure Plasma Jets

Atomic Rare Gas Metastable Monitoring through Nitrogen Emission in Atmospheric Pressure Plasma Jets

Signatures of Electronic Structure in Bicircular High-Harmonic Spectroscopy.

High-harmonic spectroscopy driven by circularly polarized laser pulses and their counterrotating second harmonic is a new branch of attosecond science which currently lacks quantitative interpretations. We extend this technique to the midinfrared regime and record detailed high-harmonic spectra of several rare-gas atoms. These results are compared with the solution of the Schrödinger equation in three dimensions and calculations based on the strong-field approximation that incorporate accurate scattering-wave recombination matrix elements. A quantum-orbit analysis of these results provides a transparent interpretation of the measured intensity ratios of symmetry-allowed neighboring harmonics in terms of (i)a set of propensity rules related to the angular momentum of the atomic orbitals, (ii)atom-specific matrix elements related to their electronic structure, and (iii)the interference of the emissions associated with electrons in orbitals corotating or counterrotating with the laser fields. These results provide the foundation for a quantitative understanding of bicircular high-harmonic spectroscopy.

Demonstration of a CW diode-pumped Ar metastable laser operating at 4 W.

Optically pumped rare gas lasers are being investigated as potential high-energy, high beam quality systems. The lasing medium consists of rare gas atoms (Rg=Ne, Ar, Kr, or Xe) that have been electric discharge excited to the metastable np5(n+1)s P32 state. Following optical excitation, helium (He) at pressures of 200-1000Torr is used as the energy transfer agent to create a population inversion. The primary technical difficulty for this scheme is the discharge production of sufficient Rg* metastables in the presence of >200 Torr of He. In this Letter, we describe a pulsed discharge that yields >1013 cm-3Ar* in the presence of He at total pressures up to 750Torr. Using this discharge, a diode-pumped Ar* laser providing 4.1W has been demonstrated.

Production of Ar and Xe metastables in rare gas mixtures in a dielectric barrier discharge

Optically pumped all-rare-gas lasers (OPRGL) utilize metastable atoms of the heavier rare gases as lasing species. The required number density of metastables for efficient laser operation is 1012–1013 cm−3 in He buffer gas at pressures in the 400–1000 Torr range. Such metastable densities are easily produced in a nanosecond pulsed discharge, even at pressures larger than atmospheric, but problems appear when one is trying to achieve continuous production. The reason for low production efficiency in many types of continuous discharge at atmospheric pressure is the low value of the E/N parameter (<5–6 Td). In the present work, we have examined the possibility of using a dielectric barrier discharge (DBD) to provide near continuous, high densities of Ar and Xe metastables. Experiments were performed using a 20 kHz DBD in binary Ar and Xe mixtures with He, and in ternary Ar:Xe:He mixtures at pressures up to 1 atmosphere. Concentrations were measured by means of tunable diode laser absorption spectroscopy. Time-averaged [Ar(1s5)] and [Xe(1s5)] number densities on the order of 1012 cm−3 were readily achieved. The temporal behavior of [Xe(1s5)] throughout the DBD cycle was observed. The results demonstrate the feasibility of using DBDs for OPRGL development. Spectral scans over the absorption lines were also used to examine the pressure broadening coefficients for the 912.3 nm Ar line in He and the Xe 904.5 nm line in Ne and He.

IR Spectroscopy of Protonated Acetylacetone and Its Water Clusters: Enol-Keto Tautomers and Ion→Solvent Proton Transfer.

Protonated ions of acetylacetone, H+(Hacac), and their argon-tagged analogues are produced via a pulsed discharge and cooled in a supersonic expansion. These ions are mass analyzed, selected in a time-of-flight spectrometer, and studied with infrared laser photodissociation spectroscopy using the method of rare-gas atom tagging. Computational studies at the DFT/B3LYP level are employed to elucidate the structures and spectra of these ions, which are expected to exist as either enol- or keto-based tautomers. The protonated acetylacetone ion is found to form a single enol-based isomer. Adding one or two water molecules to this ion, for example, H+(Hacac)(H2O)1,2, produces primarily enol-based structures, although a small concentration of keto structures also contribute to the spectra. The vibrational patterns resulting from hydrogen bonding in these systems are not well-described by theory. Addition of a third water molecule to form the H+(Hacac)(H2O)3 ion causes a significant change in the spectroscopy, attributed to proton transfer from the H+(Hacac) ion into the water solvent.

The nature of three-body interactions in DFT: Exchange and polarization effects.

We propose a physically motivated decomposition of density functional theory (DFT) 3-body nonadditive interaction energies into the exchange and density-deformation (polarization) components. The exchange component represents the effect of the Pauli exclusion in the wave function of the trimer and is found to be challenging for density functional approximations (DFAs). The remaining density-deformation nonadditivity is less dependent upon the DFAs. Numerical demonstration is carried out for rare gas atom trimers, Ar2-HX (X = F, Cl) complexes, and small hydrogen-bonded and van der Waals molecular systems. None of the tested semilocal, hybrid, and range-separated DFAs properly accounts for the nonadditive exchange in dispersion-bonded trimers. By contrast, for hydrogen-bonded systems, range-separated DFAs achieve a qualitative agreement to within 20% of the reference exchange energy. A reliable performance for all systems is obtained only when the monomers interact through the Hartree-Fock potential in the dispersion-free Pauli blockade scheme. Additionally, we identify the nonadditive second-order exchange-dispersion energy as an important but overlooked contribution in force-field-like dispersion corrections. Our results suggest that range-separated functionals do not include this component, although semilocal and global hybrid DFAs appear to imitate it in the short range.

Rotational energy transfer in collisions of ammonia with rare gas atoms and H2

SynopsisWe investigate inelastic collisions of ammonia NH3 and its isotopologue ND3 with rare gas atoms or molecular hydrogen. We use state of the art ab initio potential energy surfaces to study the low energy dynamics of the collision by means of the quantum-mechanical close-coupling method. We discuss the experimental implications of our work.

Long-range dispersion interactions between excited states of K and rare-gas atoms

SynopsisThe long range dispersion coefficients between the ground state of rare gas atoms and low-lying states of K are calculated by using relativistic method, in which the spin-orbital interactions are included.

Ortho-para interconversion in cation-water complexes: The case of V+(H2O) and Nb+(H2O) clusters.

Vanadium and niobium cation-water complexes, V+(H2O) and Nb+(H2O), are produced by laser vaporization in a pulsed supersonic expansion, mass selected in a time-of-flight spectrometer, and studied with infrared photodissociation spectroscopy using rare gas atom (Ar, Ne) complex predissociation. The vibrational bands measured in the O-H stretching region contain K-type rotational sub-band structure, which provides insight into the structures of these complexes. However, rotational sub-bands do not exhibit the simple patterns seen previously for other metal ion-water complexes. The A rotational constants are smaller than expected and the normal 3:1 intensity ratios for K = odd:even levels for independent ortho:para nuclear spin states are missing for some complexes. We relied on highly correlated internally contracted multi-reference configuration interaction and Coupled Cluster [CCSD(T)] electronic structure calculations of those complexes with and without the rare gas atoms to investigate these anomalies. Rare gas atoms were found to bind via asymmetric motifs to the hydrated complexes undergoing large amplitude motions that vibrationally average to the quasi-C2v symmetry with a significant probability off the C2 axis, thus explaining the reduced A values. Both vanadium and niobium cations exhibit unusually strong nuclear spin coupling to the hydrogen atoms of water, the values of which vary with their electronic state. This catalyzes ortho-para interconversion in some complexes and explains the rotational patterns. The rate of ortho-para relaxation in the equilibrated complexes must therefore be greater than the collisional cooling rate in the supersonic expansion (about 106 s-1).

Long-range dispersion interactions between Li and rare-gas atoms

The energy levels, oscillator strength and dipole scalar polarizabilities of Li atoms are calculated by using the relativistic semiempirical-core-potential method (RCICP). The dispersion coefficients C 6 between ground 2s 1/2 2p 1/2,2p 3/2 states of Li atom and the ground state of rare gas atoms (Ne, Ar, Kr, Xe) are calculated in JJ coupled states, in which the spin-orbital interactions are included. Present results are in good agreement with other available results.

Theoretical investigation of the weak interactions of rare gas atoms with silver clusters by resonance Raman spectroscopy modeling

AbstractThe interactions of rare gas atoms (Rg = Ar, Kr, and Xe) with small neutral and cationic silver clusters have been investigated by density functional methods and the effect of these weak interactions on the resonance Raman spectra of the complexes has been evaluated. The resonance Raman technique that depends on the properties of ground and excited state, seems deeply sensitive to the weak rare gas–metal cluster interactions, and the use of inert gases has been proven to be an excellent approach to recognize the ability of this technique to detect extremely weak interactions. In this work, for , and complexes the IR, normal and resonance Raman spectra have been calculated and the effect of rare gas–cluster stretching vibration ( ) on the pattern and the relative intensities of different spectra have been investigated. The resonance Raman spectra for the weakly interacted complexes (with the interaction energies less than −2.0 kcal/mol) exhibit the vibration with the detectable intensity that its intensity increases by going from Ag6–Ar to Ag6–Xe complex. Moreover, the resonance Raman spectra (based on the excited state gradient approximation) for high intensity nearly degenerate excited states, proved the effect of accumulation of the excited state charge density on the relative intensity of vibration.

Spectral Analysis of Moderately Charged Rare-Gas Atoms

This article presents a review concerning the spectral analysis of several ions of neon, argon, krypton and xenon, with impact on laser studies and astrophysics that were mainly carried out in our collaborative groups between Argentina and Brazil during many years. The spectra were recorded from the vacuum ultraviolet to infrared regions using pulsed discharges. Semi-empirical approaches with relativistic Hartree–Fock and Dirac-Fock calculations were also included in these investigations. The spectral analysis produced new classified lines and energy levels. Lifetimes and oscillator strengths were also calculated.

Comparative investigation of pure and mixed rare gas atoms on coronene molecules.

Clusters formed by the combination of rare gas (RG) atoms of He, Ne, Ar, and Kr on coronene have been investigated by means of a basin-hopping algorithm and path integral Monte Carlo calculations at T = 2 K. Energies and geometries have been obtained and the role played by the specific RG-RG and RG-coronene interactions on the final results is analysed in detail. Signatures of diffuse behavior of the He atoms on the surface of the coronene are in contrast with the localization of the heavier species, Ar and Kr. The observed coexistence of various geometries for Ne suggests the motion of the RG atoms on the multi-well potential energy surface landscape offered by the coronene. Therefore, the investigation of different clusters enables a comparative analysis of localized versus non-localized features. Mixed Ar-He-coronene clusters have also been considered and the competition of the RG atoms to occupy the docking sites on the molecule is discussed. All the obtained information is crucial to assess the behavior of coronene, a prototypical polycyclic aromatic hydrocarbon clustering with RG atoms at a temperature close to that of interstellar medium, which arises from the critical balance of the interactions involved.

Precision measurements of cross-sections for inelastic processes in collisions of alkali metal ions with atoms of rare gases

A multifaceted experimental study of collisions of Na[Formula: see text] and K[Formula: see text] ions in the energy range of 0.5–10 keV with He and Ar atoms is presented. Absolute cross-sections for charge-exchange, ionization, stripping and excitation processes were measured using a refined version of the transfer electric field method, angle- and energy-dependent collection of product ions, energy loss and optical spectroscopy methods. The experimental data and the schematic correlation diagrams are employed to analyze and determine the mechanisms for these processes.

Theoretical study of Si+(2PJ)–RG complexes and transport of Si+(2PJ) in RG (RG = He–Ar)

ABSTRACTWe calculate accurate interatomic potentials for the interaction of a singly charged silicon cation with a rare gas atom of helium, neon or argon. We employ the RCCSD(T) method, and basis sets of quadruple-ζ and quintuple-ζ quality; each point is counterpoise-corrected and extrapolated to the basis set limit. We consider the lowest electronic state of the silicon atomic cation, Si+(2P), and calculate the interatomic potentials for the terms that arise from this: 2Π and 2Σ+. We additionally calculate the interatomic potentials for the respective spin-orbit levels, and examine the effect on the spectroscopic parameters; we also derive effective ionic radii for C+ and Si+. Finally, we employ each set of potentials to calculate transport coefficients, and compare these to available data for Si+ in He.

Frequency-dependent dielectric function of semiconductors with application to physisorption

The dielectric function is one of the most important quantities that describes the electrical and optical properties of solids. Accurate modeling of the frequency-dependent dielectric function has great significance in the study of the long-range van der Waals (vdW) interaction for solids and adsorption. In this work, we calculate the frequency-dependent dielectric functions of semiconductors and insulators using the $GW$ method with and without exciton effects, as well as efficient semilocal density functional theory (DFT), and compare these calculations with a model frequency-dependent dielectric function. We find that for semiconductors with moderate band gaps, the model dielectric functions, $GW$ values, and DFT calculations all agree well with each other. However, for insulators with strong exciton effects, the model dielectric functions have a better agreement with accurate $GW$ values than the DFT calculations, particularly in high-frequency region. To understand this, we repeat the DFT calculations with scissors correction, by shifting DFT Kohn-Sham energy gap to match the experimental band gap. We find that scissors correction only moderately improves the DFT dielectric function in low-frequency region. Based on the dielectric functions calculated with different methods, we make a comparative study by applying these dielectric functions to calculate the vdW coefficients ($C_3$ and $C_5$) for adsorption of rare-gas atoms on a variety of surfaces. We find that the vdW coefficients obtained with the nearly-free electron gas-based model dielectric function agree quite well with those obtained from the $GW$ dielectric function, in particular for adsorption on semiconductors, leading to an overall error of less than 7% for $C_3$ and 5% for $C_5$. This demonstrates the reliability of the model dielectric function for the study of physisorption.

Conformational landscape of the SF6 dimer as revealed by high resolution infrared spectroscopy and complexation with rare gas atoms.

Taking advantage of a versatile set-up, combining pulsed pin hole or slit nozzle supersonic expansion with an external cavity quantum cascade laser, the rovibrational absorption spectrum of the SF6 dimer in the ν3 mode region has been revisited at high resolution under various experimental conditions in SF6:He mixtures. Two new rotationally resolved spectral bands have been identified in the range of the parallel band of the dimer spectrum in addition to that previously reported. Among these three spectral features, two of them are assigned to conformations of the dimer (noted #1 and #2), clearly distinguished from their different S-S interatomic distances, i.e. 474 and 480 pm respectively. The third one is assigned to a (SF6)2-He complex, from comparison with additional experiments in which (SF6)2-Rg heterotrimers (Rg = Ne, Ar, Kr, Xe) are observed. A schematic picture of the potential energy landscape of the SF6 dimer in terms of a nearly flat surface is proposed to account for the conformational relaxation observed in the expansions and for the structure of the (SF6)2-Rg heterotrimers, which are exclusively formed from the conformer #2 dimer. Although modelling qualitatively supports this picture, much effort has still to be achieved from a theoretical point of view to reach a quantitative agreement with the present benchmark experimental data both in terms of structure and energetics.

An Ab Initio Study on Four Low-lying Electronic Potential Energy Curves for Atomic Cesium and Rare Gas Pairs

Using multireference configuration interaction (MRCI) calculations with single and double excitation levels, Davidson correction, and a spin–orbit (SO) effective core potential, we have developed a series of four low-lying electronic potential energy curves (PECs) for the pairs formed between a cesium atom (Cs) and a rare gas (Rg = He, Ne, Ar, Kr, and Xe). The results obtained at the MRCI level were compared with those generated at the SOCI level, which were recently reported by Blank et al. The shapes of the PECs were essentially the same when the same basis set was used. Based on this agreement, more precise PECs for Cs–Rg pairs were calculated using a larger basis set for Rg.

Van der Waals potential energy surfaces from the exchange-hole dipole moment dispersion model

The potential energy surfaces (PESs) of 28 simple van der Waals complexes, each consisting of a rare-gas (Rg) atom interacting with a linear molecule, are calculated using the exchange-hole dipole moment (XDM) dispersion model in conjunction with three base density functionals (HFPBE, PW86PBE, and a commensurate hybrid functional). Results are compared with literature coupled-cluster reference data. The quality of the computed PESs is assessed based on the positions of the global minima and the corresponding binding energies. Only the hybrid functional is found to provide generally reliable PESs. Dispersion-corrected HFPBE strongly underestimates the equilibrium intermolecular separations and predicts different global minima than the reference PESs for Rg–HCl, Rg–HBr, and two of the Rg–HCN complexes. Analysis of the binding-energy errors reveals that the performance of HFPBE degrades as the size of the Rg atoms increase down the group, while the performance of PW86PBE is significantly worse for strongly-polar molecules. PW86PBE, and to a lesser extent the hybrid, strongly overbind Kr–HF due to charge-transfer error. Despite this, the XDM-corrected hybrid functional displays the best overall error statistics and provides binding energies to within ca. 10 cm–1 of the coupled-cluster reference data at a greatly reduced computational cost.

Influence of Defects on Vibrational Characteristics of Linear Chains of Inert Gases Atoms Adsorbed on Carbon Nanobundles

The study of vibrational characteristics of chains of rare gas atoms adsorbed in the grooves between nanotubes in nanobundles is reduced to the analyses of the phonon spectrum and the vibrational characteristics of linear chains of atoms in an external field. Atoms in the chain have three degrees of freedom. The analytical expressions for the vibrational characteristics of the atoms in the chain, depending on the ratio between the interatomic distance in the chain r and the equilibrium distance between atoms in the chain \(r_0\), are obtained. It is shown that at \(r<r_0\), the parameter of interatomic interaction, which determines the transverse vibrations frequencies, is negative. As a result, while the quasi-continuous spectrum band shifts to lower frequencies, the linear part of the temperature dependence of the heat capacity shifts to lower temperatures. The distance within only one pair of atoms is modified. It is the defect that can entail discrete states split off from the quasi-continuous spectrum band. The discrete levels with frequencies below the quasi-continuous spectrum band shift the linear part of the temperature dependence of the heat capacity to lower temperatures. The conditions for appearing of discrete frequency levels are obtained, and their characteristics are found.