Ab initio study of small He cluster ions He n + ,n=2, 3, 4, 5, and low-lying Rydberg states of He4

SCF and CEPA calculations are applied to study the structure of small He cluster ions, He _n ⁺ ,n=2, 3, 4, 5 and some low-lying Rydberg states of He₄. The effect of electron correlation upon the equilibrium structures and binding energies is discussed. He ₃ ⁺ has a linear symmetric equilibrium geometry with a bond length of 2.35a ₀ and a binding energyD _e =0.165 eV with respect to He ₂ ⁺ +He (experimentally:D ₀=0.17 eV which corresponds toD _e ≈0.20 eV). He ₄ ⁺ is a very floppy molecular ion with several energetically very similar geometrical configurations. Our CEPA calculations yield a T-shaped form with a He ₃ ⁺ centre (R _e = 2.35a ₀) and one inductively bound He atom (4.39a ₀ from the central He atom of He ₃ ⁺ ) as equilibrium structure. Its binding energy with respect to He ₃ ⁺ +He is 0.031 eV. A linear symmetric configuration consisting of a He ₂ ⁺ centre with a bond length of 2.10a ₀ and two inductively bound He atoms (4.20a ₀ from the centre of He ₂ ⁺ ) is only 0.02–0.03 eV higher in energy. We expect that in larger He cluster ions structures with He ₂ ⁺ and He ₃ ⁺ centres andn?2 orn?3 inductively bound He atoms have nearly the same energies. In He₄ a low-lying metastable Rydberg state (³ Π symmetry for linear He ₄ ^* ,³ B ₁ for the T-shaped form) exists which is slightly stronger bound with respect to He ₃ ^* +He than the corresponding ion.     

Damage in Y-Ba-Cu-O films produced by4He ions

The question of destructibility of an ion beam technique applied to the analysis of high temperature superconductors is discussed, namely the influence of the often used analyzing⁴He ion beam on a monocrystalline YBa₂Cu₃O₇ film. The rate of irradiation defect production is measured for 1 and 3.07 MeV⁴He⁺ irradiation and compared with a Monte Carlo simulation. It is shown that the usual depth profiling by⁴He ion beams does not change the measured element profiles, but is destructive from the view point of the superconducting properties of a sample, due to the great number of defects produced. Using a large solid angle detector one can minimize the analyzing dose to avoid the destruction of superconducting properties.     

3He-3He drop collisions in the Vlasov dynamics

We have investigated the collision of³He drops in the normal phase by means of the Vlasov equation. The structure and dynamics of the drops have been described by a density functional that takes properly into account relevant properties of the homogeneous liquid. Results for³He₂₅₀-³He₂₅₀ collisions at different energies and impact parameters are presented.     

Does He2 Exist?

For the electronic ground state X ¹Σ⁺_g, the potential-energy function of He₂ reported by Aziz et al. has been transformed into the form V(z), containing only eight parameters, which is more suitable for the investigation of the existence of states of discrete energy. We found no evidence that a bound vibration-rotational state of the stable diatomic molecule ³He₂ or ⁴He₂, even if rotating, can exist in the electronic ground state.     

He2@C60: Thoughts of the concept of a molecule and of the concept of a bond in quantum chemistry

We present a broad palette of discussions of the concepts of a molecule and a chemical bond that always lay down behind all computational modeling in quantum chemistry and of the endohedral fullerene He₂@C₆₀ in particular. For this purpose, we offer the definition of quantum chemistry as composed of three ingredients. Each of them is illustrated by its particular concept, either that of a molecule or a bond. The third, computational ingredient is tackled to resolve the bonding manifold of He₂@C₆₀ and to demonstrate that van‐der‐Waals binding of He? He is converted within He₂@C₆₀ into a stronger bond due to that C₆₀ acts as an electronic buffer and [He₂] moiety mimics a fractionally charged . Experimental fingerprints of He₂@C₆₀ are computed. © 2015 Wiley Periodicals, Inc.     

Doubly-excited 1,3Po autoionization states of He between the N = 4 and N = 6 thresholds of He+ ions

The method of complex-coordinate rotation is used to investigate the doubly-excited ^1,3P^o autoionization states of He between the N = 4 and N = 6 thresholds of He⁺ ions. Resonance energies and total widths for 51 ¹P^o and 51 ³P^o states are reported in the present work. For the singletspin and triplet-spin states, lower-lying resonances for all nine Rydberg series converging on the He⁺ (N = 5) threshold are calculated. For resonances below the He⁺ (N = 6) threshold, we report lower-lying states for eleven and ten Rydberg series for the singlet-spin states and triplet-spin states, respectively. Our results are compared with the experimental observations and with other theoretical calculations when available.     

Electron loss and capture to continuum from He and Ne atoms bombarded with He+-Ions

We have measured the cusp electron yield in coincidence with the transmitted charge state (He⁰, He⁺ and He⁺⁺) when³He⁺ collides with He and Ne under single collision conditions. For the first time this enables the electron capture to the continuum (ECC) yield to be directly compared with that from electron loss to continuum (ELC). While the ECC contribution is smaller than that from ELC at high projectile velocities (V _p >3 au) the data suggest that ECC will dominate belowV _p =2.8 au. The relevance of the results to the projectile velocity dependence of existing capture theories is discussed.     

Recoil-ion momentum distribution for He(e,2e)He+-and He(e,3e)He++-reactions

Using Recoil-Ion Momentum Spectroscopy (RIMS) we have measured the momenta of recoiling target ions in He(e,2e)He⁺- and He(e,3e)He⁺⁺-reactions at impact energies between 270 ev and 3200 eV. The recoil-ion momentum reflecting the sum momentum of all outgoing electrons was determined for the first time in all three spatial dimensions separately for single and double ionization by electron impact. The data are compared to results of a nCTMC-calculation.     

3He Impurities in Nearly Frictionless Transport of Solid 4He at Low Temperatures

Glassy matter, when subjected to high shear rates exhibit shear thinning, that is, the viscosity diminishes with increasing shear rate. One possible outcome for the almost vanishing viscosity is nearly frictionless transport, which is possible in solid ⁴He due to the presence of minute concentrations of ³He. The glassy state of solid ⁴He is also relevant to the possible onset of superuidity in solid ⁴He. By treating the solid ⁴He locally as an amorphous matter and using the transition‐rate dependent model together with the specific activation energy, we observe a series of sudden changes of the shearing stresses (which directly relates to the resistance) at corresponding onset temperatures of supersolid ⁴He (ranging from 175 to 1200 mK) for different activation volumes of ³He. Even at higher concentrations of ³He than previous reported (around 1700 ppm), the supersolidity of ⁴He still occurs.     

83Kr nuclear magnetic moment in terms of that of 3He

High resolution NMR spectroscopy was applied to precisely determine the ⁸³Kr nuclear magnetic dipole moment on the basis of new results available for nuclear magnetic shielding in krypton and helium‐3 atoms. Small amounts of ³He as the solutes and ⁸³Kr as the buffer gas were observed in ³He and ⁸³Kr NMR spectra at the constant external field, B₀ = 11.7578 T. In each case, the resonance frequencies (ν^He and ν^Kr) were linearly dependent on the density of gaseous solvent. The extrapolation of experimental points to the zero density of gaseous krypton allowed for the evaluation of both resonance frequencies free from intermolecular interactions. By combining these measurements with the recommended ⁸³Kr chemical shielding value, the nuclear magnetic moment could be determined with much better precision than ever before, μ(⁸³Kr) = ?0.9707297(32)μ_N, with the improvement due to the greater accuracy of the spectral data. Copyright © 2014 John Wiley & Sons, Ltd.     

3He impurities on4He clusters

³He impurities on⁴He clusters form surface bound states analogous to the Andreev states on a planar liquid-gas interface. The energies and wave functions of such states are evaluated using the Feynman-Lekner variational theory as well as a density functional method, previously employed for the planar surface case. The two methods give similar results. The spectrum of the impurity states is studied as a function of the cluster dimension.     

Molecular view of charge exchange in ion–C60 collisions

We present a theoretical study of charge transfer in H⁺+C₆₀ and He²⁺+C₆₀ collisions using an extension of the molecular time‐dependent method of ion–atom collisions. Energy‐correlation diagrams have been evaluated for the corresponding (C₆₀–H)⁺ and (C₆₀–He)²⁺ quasi‐molecules. Single and double charge‐transfer cross sections in C₆₀+He²⁺ collisions are reported for the first time. The results show that double charge‐transfer cross sections are only one order of magnitude smaller than single charge‐transfer cross sections. © 2001 John Wiley & Sons, Inc. Int J Quantum Chem, 2001     

Excitation of He—41 D-substates by He+- and Ne+-projectiles investigated by level-crossing techniques

Collisions of He⁺- and Ne⁺-projectiles with He at impact energies between 90 keV and 800 keV were investigated. Relative excitation cross sections for magnetic sublevels of He—4¹ D were determined using level-crossing techniques. Absolute excitation cross sections σ _m of the Zeeman-sublevels are given using He—4¹ D cross sections from earlier measurements. The results show strong variations of the cross sections σ₀ and σ_±1 with a quasi-oscillatory behaviour. σ_±2 is much smaller than σ₀ and σ_±1.     

Spin-orbit and spin-spin couplings in He2 and He2−

The spin-orbit and the spin-spin coupling constants of the ⁴Π_g state of the He₂ ⁻ ion, of the parent a³Σ_u ⁺, and of the b³Π_g states of He₂ have been evaluated by a multireference configuration interaction method. The theoretical spin-spin splittings of the a³Σ_u ⁺ state and the R-dependent spin-spin function are found to be in excellent agreement with experiment, with deviations in the range of a few MHz. The theoretical spin-orbit constants and splittings of the b³Π_g state are larger than the experimental values by about 370 MHz. The spin-orbit coupling constant of the ⁴Π_g state of He₂ ⁻ is␣estimated to be three times smaller than in the b³Π_g state, but one of the intramultiplet off-diagonal spin-spin interactions is predicted to give a large contribution to the fine structure of the metastable ion. The theoretical fine structure constants for the He₂ ⁻ ion are expected to␣aid future spectroscopic investigations of the fine structure splittings of the negative ion. Received: 14 April 1998 / Accepted: 27 July 1998 / Published online: 19 October 1998     

A three-dimensional finite element approach towards molecular SCF computations

Fully three-dimensional, SCF ground-state computations for the Hartree equation are carried out by a finite element approach that completely avoids forming or storing the Fock matrix. A combination of strategies is used to reduce storage and computational requirements by orders of magnitude over the traditional finite element approach, which makes three-dimensional molecular orbital computations feasible. Results using the three-dimensional formulation and computer program are shown for one-electron systems: He⁺ and H₂⁺, and for two-electron systems: He and H₂. The best results are within about 30–100 micro-Hartrees of the exact values of the total energies for the ground states of these systems, indicating that our three-dimensional approach has been correctly implemented in the computer code.     

Thermodynamic interaction functions for 4He and 3He quantum liquids

The method of interaction functions is applied to quantum liquids. The interaction energies at 0 K are found as 14.3 cal/mole for ⁴He and 11.0 cal/mole for ³He. The interaction energy as a function of volume for all temperatures along the saturation line is deduced as an expression common to the two isotopes. The two isotopes have a region of anomaly in the interaction entropy, where the liquid appears less ordered than an ideal gas. These anomalies can be eliminated for ³He by allowance for the spin entropy and for ⁴He via the difference between the concentrations of the component with zero entropy in the liquid and Bose gas.     

Intra- and inter-atomic auger processes in collisions of low energy He++, He+, He* (23,S, 21 S) and Li+ with Li covered W(110) surfaces

Electron spectra from He⁺⁺, He⁺ and Li⁺ (10 to 1500 eV) ions colliding under grazing incidence with Li covered W (110) surfaces are reported. The results are compared with those obtained from thermal collisions of (2³ S; 2¹ S) metastable He atoms. In these collisions 1s vacancies are either produced during the collision event (energetic He⁺ (Li ⁺) collisions) or are brought into the collision (slow He⁺⁺ (He⁺, He*) collisions). Population of the 2s orbitals by two electrons produces states which decay by intraatomic Auger processes: we observe autoionization of He** (2s ²) and Li** (1s 2s ²) as well as autodetachment of He^?* (1s 2s ²). Alternatively the 1s-holes in the projectile or target (Li) can be filled by Auger processes involving one or two surface electrons. The processes leading to electron emission are studied as a function of the Li coverage in the submonolayer region (0≦Θ_Li≦1Ml) and as a function of the projectile energy. It is concluded that with one or two 1s vacancies present in the projectile the double capture of two surface electrons constitutes an important process responsible for electron emission of low work function surfaces.     

Lone pairs mapping by Laplacian of 3He NMR chemical shift

Results of approbation of a new quantum mechanical approach of lone pairs (LPs) visualization, its optimization and testing on a range of model molecules are presented. The main idea of proposed methodology is using ³He atom as a probe for investigating electronic shells of species with LPs. As model objects, we consider “classical” examples of hydrogen cyanide, methanimine, ammonia, phosphine, formaldehyde, water, and hydrogen sulfide. It is shown that LPs can be visualized by means of 3D maps of Laplacian of ³He chemical shift ∇²δ_He. NMR calculations could be performed using level of theory as low as B3LYP/6-31G, allowing for the reduction of computational time without significant loss of quality. Advantages of our approach are discussed in comparison with usual methods of lone pairs visualization (electron localization function, molecular electrostatic potential).     

Energetics and Structures of Charged Helium Clusters: Comparing Stabilities of Dimer and Trimer Cationic Cores

We present accurate ab initio calculations of the most stable structures of He_n⁺ clusters in order to determine the more likely ionic core arrangements existing after reaching structural equilibrium of the clusters. Two potential energy surfaces are presented: one for the He₂⁺ and the other with the He₃⁺ linear ion, both interacting with one He atom. The two computed potentials are in turn employed within a classical structure optimization where the overall interaction forces are obtained within the sum‐of‐ potentials approximation described in the main text. Because of the presence of many‐body effects within the ionic core, we find that the arrangements with He₃⁺ as a core turn out to be energetically preferred, leading to the formation of He₃⁺(He)_n?3 stable aggregates. Nanoscopic considerations about the relative stability of clusters with the two different cores are shown to give us new information on the dynamical processes observed in the impact ionization experiments of pure helium clusters and the importance of pre‐equilibrium evaporation of the ionic dimers in the ionized clusters.