Photoionization of helium nanodroplets doped with rare gas atoms

Photoionization of He droplets doped with rare gas atoms (Rg=Ne, Ar, Kr, and Xe) was studied by time-of-flight mass spectrometry, utilizing synchrotron radiation from the Advanced Light Source from 10 to 30 eV. High resolution mass spectra were obtained at selected photon energies, and photoion yield curves were measured for several ion masses (or ranges of ion masses) over a wide range of photon energies. Only indirect ionization of the dopant rare gas atoms was observed, either by excitation or charge transfer from the surrounding He atoms. Significant dopant ionization from excitation transfer was seen at 21.6 eV, the maximum of He 2p 1P absorption band for He droplets, and from charge transfer above 23 eV, the threshold for ionization of pure He droplets. No Ne+ or Ar+ signal from droplet photoionization was observed, but peaks from HenNe+ and HenAr+ were seen that clearly originated from droplets. For droplets doped with Rg=Kr or Xe, both Rg+ and HenRg+ ions were observed. For all rare gases, Rg2+ and HenRgm+ (n,m> or =1) were produced by droplet photoionization. Mechanisms of dopant ionization and subsequent dynamics are discussed.     

Diatomic monocations and dications containing germanium and a rare gas atom.

Diatomic dications and monocations GeY2+ and GeY+, where Y = Ne, Ar, Kr or Xe, have been detected on the microsecond time scale. They are characterized via appearance energies, charge stripping of GeY+ ions, and mass-analysed ion kinetic energy spectroscopy. The formation of GeAr+ is found to involve an excited state of Ar in a Hornbeck-Molnar process.     

On the noble-gas-induced intersystem crossing for the CUO molecule: experimental and theoretical investigations of CUO(Ng)n (Ng = Ar, Kr, Xe; n = 1, 2, 3, 4) complexes in solid neon

Uranium atoms excited by laser ablation react with CO in excess neon to produce the novel CUO molecule, which forms distinct Ng complexes (Ng = Ar, Kr, Xe) when the heavier noble gases are added. The CUO(Ng) complexes are identified through CO isotopic and Ng substitution on the neon matrix infrared spectra and by comparison to DFT frequency calculations. The U-C and U-O stretching frequencies of CUO(Ng) complexes are slightly red-shifted from frequencies for the (1)Sigma(+) CUO ground state, which identifies singlet ground state CUO(Ng) complexes. In solid neon the CUO molecule is also a complex CUO(Ne)(n), and the CUO(Ne)(n-1)(Ng) complexes are likewise specified. The next singlet CUO(Ne)(x)(Ng)(2) complexes in excess neon follow in like manner. However, the higher CUO(Ne)(x)(Ng)(n) complex (n = 3, 4) stretching modes approach pure argon matrix CUO(Ar)(n) values and isotopic behavior, which are characterized as triplet ground state complexes by DFT frequency calculations. This work suggests that the singlet-triplet crossing occurs with 3 Ar, 3 Kr, or 4 Xe and a balance of Ne atoms coordinated to CUO in the neon matrix host.     

State-selective preparation of NO2+ and the effects of NO2+ vibrational mode on charge transfer with NO

Two color resonance-enhanced multiphoton ionization (REMPI) scheme of NO(2) through the E (2)Sigma(u)(+) (3psigma) Rydberg state was used to prepare NO(2)(+) in its ground and (100), (010), (02(0)0), (02(2)0), and (001) vibrational states. Photoelectron spectroscopy was used to verify >96% state selection purity, in good agreement with results of Bell et al. for a similar REMPI scheme. The effects of NO(2)(+) vibrational excitation on charge transfer with NO have been studied over the center-of-mass collision energy (E(col)) range from 0.07 to 2.15 eV. Charge transfer is strongly suppressed by collision energy at E(col) < approximately 0.25 eV but is independent of E(col) at higher energies. Mode-specific vibrational effects are observed for both the integral and differential cross-sections. The NO(2)(+) bending vibration strongly enhances charge transfer, with enhancement proportional to the bending quantum number, and is not dependent on the bending angular momentum. The enhancement results from increased charge transfer probability in large impact parameter collisions that lead to small deflection angles. The symmetric stretch also enhances reaction at low collision energies, albeit less efficiently than the bend. The asymmetric stretch has virtually no effect, despite being the highest-energy mode. A model is proposed to account for both the collision energy and the vibrational state dependence.     

Optimal covering of C(60) fullerene by rare gases

Putative global energy minima of clusters formed by the adsorption of rare gases on a C(60) fullerene molecule, C(60)X(N) (X=Ne, Ar, Kr, Xe; N ≤ 70), are found using basin-hopping global optimization in an empirical potential energy surface. The association energies per rare gas atom as a function of N present two noticeable minima for Ne and Ar and just one for Kr and Xe. The minimum with the smallest N is the deepest one and corresponds to an optimal packing monolayer structure; the other one gives a monolayer with maximum packing. For Kr and Xe, optimal and maximum packing structures coincide. By using an isotropic average form of the X-C(60) interaction, we have established the relevance of the C(60) surface corrugation on the cluster structures. Quantum effects are relevant for Ne clusters. The adsorption of these rare gases on C(60) follows patterns that differ significantly from the ones found recently for He by means of experimental and theoretical methods.     

L X-ray emission from fast highly charged Cu ions in collisions with gaseous targets: Saturation effect in excitation and transfer

We have measured L X-ray production cross sections for highly charged 156 MeV Be-like Cu ions in collisions with gaseous targets of H₂, Ne, Ar, Kr and Xe. In the present collision systems, measured projectile L X-ray intensity is contributed by the excitation as well as electron transfer processes. The projectile L X-ray production cross sections are found to increase initially and then saturate with increasing target atomic number. The charge state dependence of projectile L X-ray production cross sections have been measured with Kr target.     

Ti2: accurate determination of the dissociation energy from matrix resonance Raman spectra and chemical interaction with noble gases

UV-visible and resonance Raman spectra of Ti(2) isolated in Ar, Kr, and Xe matrices at temperatures of 10 K were measured by using the 514 nm line of an Ar ion laser. The data show that the Ti(2) molecule interacts strongly with Xe, leading to a significant weakening of the Ti[bond]Ti bond strength. The f(Ti[bond]Ti) force constant decreases in the series Ar>Kr>Xe, from 232.8 Nm(-1) in Ar and 225.5 Nm(-1) in Kr to 199.7 Nm(-1) in Xe. Additional experiments in an Ar matrix containing 2 % of Xe indicate the formation of a molecule of the formula Ti(2)Xe. Our spectra for Ti(2) in an Ar matrix give evidence for several previously not observed members of the Stokes progression. The sum of experimental data allows for an improved estimation of the dissociation energy on the basis of a LeRoy-Bernstein-Lam analysis. A dissociation energy of 1.18 eV was derived from this analysis. The UV-visible data give evidence of the vibrational levels of an excited state of Ti(2).     

The C3-bending vibrational levels of the C3-Kr and C3-Xe van der Waals complexes studied by their Ã-X̃ electronic transitions and by ab initio calculations

Fluorescence excitation spectra and wavelength-resolved emission spectra of the C(3)-Kr and C(3)-Xe van der Waals (vdW) complexes have been recorded near the 2(2-)(0), 2(2+)(0), 2(4-)(0), and 1(1)(0) bands of the A?(1)Π(u)-X?(1)Σ(g)(+) system of the C(3) molecule. In the excitation spectra, the spectral features of the two complexes are red-shifted relative to those of free C(3) by 21.9-38.2 and 34.3-36.1 cm(-1), respectively. The emission spectra from the A? state of the Kr complex consist of progressions in the two C(3)-bending vibrations (ν(2), ν(4)), the vdW stretching (ν(3)), and bending vibrations (ν(6)), suggesting that the equilibrium geometry in the X? state is nonlinear. As in the Ar complex [Zhang et al., J. Chem. Phys. 120, 3189 (2004)], the C(3)-bending vibrational levels of the Kr complex shift progressively to lower energy with respect to those of free C(3) as the bending quantum number increases. Their vibrational structures could be modeled as perturbed harmonic oscillators, with the dipole-induced dipole terms of the Ar and Kr complexes scaled roughly by the polarizabilities of the Ar and Kr atoms. Emission spectra of the Xe complex, excited near the A?, 2(2-) level of free C(3), consist only of progressions in even quanta of the C(3)-bending and vdW modes, implying that the geometry in the higher vibrational levels (υ(bend) ≥ 4, E(vib) ≥ 328 cm(-1)) of the X? state is (vibrationally averaged) linear. In this structure the Xe atom bonds to one of the terminal carbons nearly along the inertial a-axis of bent C(3). Our ab initio calculations of the Xe complex at the level of CCSD(T)∕aug-cc-pVTZ (C) and aug-cc-pVTZ-PP (Xe) predict that its equilibrium geometry is T-shaped (as in the Ar and Kr complexes), and also support the assignment of a stable linear isomer when the amplitude of the C(3) bending vibration is large (υ(4) ≥ 4).     

Vibrational relaxation of NO(XΠ, υ = 1) studied by an IR-UV-double-resonance technique

Pulses from a mechanically chopped CO-laser were used to optically pump the first vibrational level of NO molecules in their fundamental band near 5.3 μm. The population of NO (υ = 1) was followed by measuring the resonance fluorescence of NO-γ-bands from a microwave discharge lamp in the UV region. Analysis of the first order decays of NO(υ = 1) following the excitation pulses yielded rate constants for V---T and V---V energy transfer processes in collisions of NO(υ = 1) with ground state NO and added gas molecules He, Ne, Ar, Kr, Xe, H₂, HD, D₂, N₂, O₂ and N₂O.     

Diatomic potential well depths from analyses of high-resolution electron energy spectra for autoionizing collision complexes

High-resolution energy spectra of electrons released in Penning ionization collisions of metastable rare gas atoms Rg*(ns) (Rg = He, Ne, Ar, Kr, Xe) with several open-shell and closed-shell atoms are analyzed to determine the well depth of the potential energy curve which describes the respective autoionizing collision complex. We thereby elucidate trends in the chemical interaction of Rg* with closed-shell target atoms A(ns ²) and establish a basis for detailed comparison with the respective interactions involving open-shell, ground state alkali atoms A(ns). From electron energy spectra due to␣associative ionization (RgH⁺ formation) in Rg* + H(1s) collisions, we determine binding energies for the RgH⁺(¹Σ) ground state potential (Rg = Ne, Ar, Kr, Xe) with uncertainties around 0.03 eV. Received: 30 June 1998 / Accepted: 5 August 1998 / Published online: 28 October 1998     

Die Photokernreaktionen der Edelgase mit 15-MeV-bremsstrahlung

The rare gases Xe, Ar, Kr and Ne under normal pressure in quartz ampoules were irradiated with 15-MeV-Bremsstrahlung for two hours in the Mikrotron (23–25 μA) of the Joint Institute of Nuclear Research Dubna. Identification of the generated radionuclides was carried out by means of measured γ-energies and half-life. The rare gases Xe, Kr and Ar except Ne are generating with 15-MeV-Bremsstrahlung several radionuclides. Relative sensitivities and detection limits for determination of rare gases are estimated and possibilities of applications are discussed.      

Experimental and theoretical studies of the effect of mass on the dynamics of gas/organic-surface energy transfer

The effect of mass on gas/organic-surface energy transfer is explored via investigation of the scattering dynamics of rare gases (Ne, Ar, and Kr) from regular (CH3-terminated) and omega-fluorinated (CF3-terminated) alkanethiol self-assembled monolayers (SAMs) at 60 kJmol collision energy. Molecular-beam scattering experiments carried out in ultrahigh vacuum and molecular-dynamics simulations based on high-accuracy potentials are used to obtain the rare-gases' translational-energy distributions after collision with the SAMs. Simulations indicate that mass is the most important factor in determining the changes in the energy exchange dynamics for Ne, Ar, and Kr collisions on CH3- and CF3-terminated SAMs at 60 kJmol collision energy. Other factors, such as changes in the gas-surface potential and intrasurface interactions, play only a minor role in determining the differential dynamics behavior for the systems studied.     

Collision-induced nonadiabatic transitions in the second-tier ion-pair states of iodine molecule: experimental and theoretical study of the I2(f0g+) collisions with rare gas atoms

Nonadiabatic transitions induced by collisions with He, Ar, Kr, and Xe atoms in the I(2) molecule excited to the f0(g)(+) second-tier ion-pair state are investigated by means of the optical-optical double resonance spectroscopy. Fluorescence spectra reveal that the transition to the F0(u)(+) state is a dominant nonradiative decay channel for f state in He, Ar, and Kr, whereas the reactive quenching is more efficient for collisions with Xe atom. Total rate constants and vibrational product state distributions for the f-->F electronic energy transfer are determined and analyzed in terms of energy gaps and Franck-Condon factors for the combining vibronic levels at initial vibrational excitations v(f)=8, 10, 14, and 17. Quantum scattering calculations are performed for collisions with He and Ar atoms, implementing a combination of the diatomics-in-molecule and long-range perturbation theories to evaluate diabatic PESs and coupling matrix elements. Calculated rate constants and vibrational product state distributions agree well with the measured ones, especially in case of Ar. Qualitative comparison is made with the previous results for the second-tier f0(g)(+)-->F0(u)(+) transition in collisions with I(2)(X) molecule and the first-tier E0(g)(+)-->D0(u)(+) transition induced by collisions with the rare gas atoms.     

Theoretical studies on the potential energy surfaces and vibrational energy levels of HXeF and HXeCl

The potential energy surfaces for the electronic ground state of the HXeCl and HXeF molecules areconstructed by using the internally contracted multi-reference configuration interaction with theDavidson correction(icMRCI Q)method and large basis sets.The stabilities and dissociation barriersare identified from the potential energy surfaces.The three-body dissociation channel is found to bethe dominate dissociation channel for HXeCl,while two dissociation channels are possible and com-petitive for HXeF.Based on the obtained potentials,vibrational energy levels of HXeCl and HXeF arecalculated using the Lanczos algorithm.Our theoretical results are in good agreement with the avail-able observed values.Particularly,the calculated fundamental frequency of the H—Xe stretching vi-bration including the Xe matrix effect of HXeCl is found to be 1666.6 cm-1,which is only 17.6 cm-1higher than the recently observed value of 1649 cm-1.     

Calculation of transport properties and intermolecular potential energy function of the binary mixtures of H2 with Ne,Ar, Kr and Xe by a semi-empirical inversion method

The present paper contains inspection of the improved corresponding states principle for transport properties of hydrogen and the binary mixtures of hydrogen with Ne, Ar, Kr and Xe. The set of corresponding states parameters has been defined by a complex numerical analysis of a carefully selected body of experimental data. The obtained correlations for the reduced orientation-averaged diffusion and viscosity collision integrals are restricted to low densities in a temperature range from T = ?/k to the onset of ionization. These equations have been inverted directly to give the isotropic and effective intermolecular potential energy curve for binary mixtures of H₂ with Ne, Ar, Kr and Xe corresponding to the viscosity collision integrals. The results are then used to obtain the best Morse-Spline-Van der Waals (MSV) potential parameters. Our inverted potential energies have been compared with experimental intermolecular potentials that were obtained by molecular beam scattering and infrared spectroscopic measurements. In this research, the Chapman–Enskog and Wang Chang-Uhlenbeck-de Boer (WCUB) version of kinetic theory have been used in conjunction with our inverted potential energies to reproduce viscosity, diffusion, thermal conductivity and thermal diffusion factor of binary mixtures of H₂ with Ne, Ar, Kr and Xe in a wide temperature range for equimolar composition. As the deviation plots illustrate, our obtained intermolecular potential energies (on the basis of the algorithm presented in the inversion process) represent the low-density transport properties of binary mixtures of H₂ with Ne, Ar, Kr and Xe within their expected experimental uncertainties. Close agreement between the predicted values and the literature results of transport properties demonstrates the predictive power of the inversion scheme.     

Absorption spectra of e-beam-excited Ne, Ar, and Kr, pure and in binary mixtures

A technique using the broadband emission of a laser plume as probe radiation is applied to record UV-visible (190-510 nm) absorption spectra of Ne, Ar, and Kr, pure and in binary mixtures under moderate e-beam excitation up to 1?MW/cm(3). In all the rare gases and mixtures, the absorption spectra show continuum related to Rg(2) (+) homonuclear ions [peaking at λ～285, 295, and 320 nm in Ne, Ar, and Kr(Ar/Kr), respectively] and a number of atomic lines related mainly to Rg(?)(ms) levels, where m is the lowest principal quantum number of the valence electron. In argon, a continuum related to Ar(2) (?) (λ～325?nm) is also recorded. There are also trains of narrow bands corresponding to Rg(2) (?)(npπ?(3)Π(g))←Rg(2) (?)(msσ?(3)Σ(u) (+)) transitions. All the spectral features mentioned above were reported in literature but have never been observed simultaneously. Although charge transfer to a homonuclear ion of the heavier additive is commonly believed to dominate in binary rare-gas mixtures, it is found in this study that in Ne/Kr mixture, the charge is finally transferred from the buffer gas Ne(2) (+) ion not to Kr(2) (+) but to heteronuclear NeKr(+) ion.     

Bonding of multiple noble-gas atoms to CUO in solid neon: CUO(Ng)n (Ng=Ar, Kr, Xe; n=1, 2, 3, 4) complexes and the singlet-triplet crossover point

Laser-ablated U atoms co-deposited with CO in excess neon produce the novel CUO molecule, which forms distinct Ng complexes (Ng=Ar, Kr, Xe) with the heavier noble gases. The CUO(Ng) complexes are identified through CO isotopic and Ng reagent substitution and comparison to results of DFT frequency calculations. The U[bond]C and U[bond]O stretching frequencies of CUO(Ng) complexes are slightly red-shifted from neon matrix (1)Sigma(+) CUO values, which indicates a (1)A' ground state for the CUO(Ng) complexes. The CUO(Ng)(2) complexes in excess neon are likewise singlet molecules. However, the CUO(Ng)(3) and CUO(Ng)(4) complexes exhibit very different stretching frequencies and isotopic behaviors that are similar to those of CUO(Ar)(n) in a pure argon matrix, which has a (3)A" ground state based on DFT vibrational frequency calculations. This work suggests a coordination sphere model in which CUO in solid neon is initially solvated by four or more Ne atoms. Up to four heavier Ng atoms successively displace the Ne atoms leading ultimately to CUO(Ng)(4) complexes. The major changes in the CUO stretching frequencies from CUO(Ng)(2) to CUO(Ng)(3) provides evidence for the crossover from a singlet ground state to a triplet ground state.     

The absorption and excitation spectroscopy of matrix-isolated atomic manganese: sites of isolation in the solid rare gases

This study collects information from absorption and luminescence excitation spectra recorded for Mn atoms isolated in the solid rare gases Ar, Kr, and Xe and presents an analysis of the site occupancy, based on the polarizabilities of the rare gases and the observed spectral shifts. Two thermally stable sites of isolation exist for atomic Mn in solid Ar and Kr, while a single thermally stable site is present in Mn/Xe. Site occupancy assignments are based on the application of a polarizability model to the z (6)P(5/2)<--a (6)S(5/2); z (8)P(5/2)<--a (6)S(5/2), and y (6)P(5/2)<--a (6)S(5/2) electronic transitions of atomic Mn. From an analysis of the observed RG matrix-to-gas phase energy shifts for P<--S type transitions, this model allows the association of certain site types occupied by metal atoms in the rare gas solids. The required condition being a linear dependence of the matrix shifts with rare gas polarizability for those metal atoms "trapped" in a particular site type. Application of the polarizability model in conjunction with trends observed in site dominance, established a connection between the blue sites in Ar and Kr and the single site in Xe. Use of the known MgRG ground state bond lengths facilitated an identification of the sites of Mn atom isolation assuming the transference of the known MgRG bond lengths to the MnRG systems. Substitutional site occupancy of atomic Mn is assigned to the blue sites in Ar and Kr and the single site in Xe, while tetra-vacancy site occupancy is assigned to the red sites in Ar and Kr. Consistent with these assignments, Mn atoms in solid Ar show a preference for trapping in tetra-vacancy sites whereas in solid Kr, single substitutional sites are preferred and in Xe, this is the only site observed.     

Theoretical Study of Rg·NO (Rg=He,Ne, Ar and Kr) Complexes

Rg·NO (Rg=He, Ne, Ar and Kr) complexes were studied using ab initio calculations. The neutral Rg·NO complex geometry and vibrational frequencies were calculated with the cc-pVDZ basis set at the CCSD(T) level of theory. The calculations show that the geometry of the Rg·NO complexes is a skewed T-shape with the Rg atom on the oxygen side of the NO molecule, and that the RgNO bond angle increases with mass. The dissociation energies (DE) and ionization energies (IE) of the neutral Rg·NO complexes, and the dissociation energies of Rg·NO+ ionic complexes were calculated using Gaussian-2 (G2) methods and a high accuracy energy model. The ionization energies of the neutral Rg·NO complexes range from 9.265 eV for He·NO to 9.132 eV for Kr·NO and the dissociation energies of Rg·NO+ range from 0.017 eV for He·NO+ to 0.156 eV for Kr·NO+, in line with the expectation based on the increasing polarizability of the Rg atom.