Path Integral Hybrid Monte Carlo Study on Structure of Small Helium-4 Clusters Doped with a Linear Molecule

Microscopic structure of small helium-4 clusters doped with a carbonyl sulfide molecule, OCS(⁴He) _N , at 0.37 K is studied by the path integral hybrid Monte Carlo method; the size of the cluster N ranges from N=2 to N=5. In all the cases examined in the present study, the helium atoms are localized around the carbon atom of the OCS molecule, forming a doughnut-type structure around the molecular axis. Bosonic exchange among the helium atoms is found to be promoted in the doughnut region, showing an anisotropic “superfluid” response of the clusters.     

Structure and Energetics of Helium Adsorption on Nanosurfaces

The ground and excited state properties of small helium clusters, ⁴He _N , containing nanoscale (～3–10 Å) planar aromatic molecules have been studied with quantum Monte Carlo methods. Ground state structures and energies are obtained from importance-sampled, rigid-body diffusion Monte Carlo. Excited state energies due to helium vibrational motion are evaluated using the projection operator, imaginary time spectral evolution technique. We examine the adsorption of N helium atoms (N≤24) on a series of planar aromatic molecules (benzene, naphthalene, anthracene, tetracene, phthalocyanine). The first layer of helium atoms is well-localized on the molecule surface, and we find well-defined localized excitations due to in-plane vibrational motion of helium on the molecule surface. We discuss the implications of these confined excitations for the molecule spectroscopy.     

Spin exchange rate constant for collisions of metastable helium atoms with rubidium atoms

The spin exchange rate constant C _se in the He(2³S₁)-Rb(5²S_1/2) system has been measured for the first time in experiments on the optical orientation of metastable helium atoms in the presence of rubidium atoms. In the temperature interval T = 293–348 K, this value is C _se = (1.8 ± 0.4) × 10^?9 cm³ s^?1. The chemiionization rate constant, which has been simultaneously measured in collisions of these particles, is C _ci = (3.1 ± 0.6) × 10^?9 cm³ s^?1.     

Adsorption of3He and4He on copper and on argon-coated copper below 20 K

Measurements have been made of adsorption isotherms of ³ He and of ⁴ He on copper and on a monolayer of argon deposited on copper in the temperature range 6.18–18.55 K and in the pressure range 0.25 to 75 Torr. From these many isotherms, calculations have been made of the isosteric heat of adsorptionQ _st/R. In the limit of zero coverage on the argon monolayerQ _st/R=76±2 K for ³ He and 76±2 K for ⁴ He. For adsorption on the bare copper,Q _st/R is difficult to extrapolate to zero coverage, but it probably lies (for both ³ He and ⁴ He) between 135 and 165 K. At theoretical monolayer helium coverage,Q _st/R=44±2 K for ³ He on the argon monolayer and 47±2 K for ⁴ He. At theoretical monolayer helium coverage on the bare copper,Q _st/R=61±4 K for ³ He and 77±5 K for ⁴ He. The results are compared with theoretical evaluations for helium adsorbed on an argon monolayer and with some previous experimental data, and the agreement is found to be fair. All the data are summarized in tables. Finally, a review is given of evaluations, including those from this work, of the monolayer capacity of ³ He and ⁴ He on the substrates studied.Work supported by a contract with the Department of Defense (Themis Program) and with the Office of Naval Research and by a Grant from the National Science Foundation.     

Evidence for a Self-bound Liquid State and the Commensurate–Incommensurate Coexistence in 2D 3He on Graphite

We made heat-capacity measurements of two dimensional (2D) ³He adsorbed on graphite preplated with monolayer ⁴He in a wide temperature range (0.1≤T≤80 mK) at densities higher than that for the 4/7 phase (=6.8 nm^?2). In the density range of 6.8≤ρ≤8.1 nm^?2, the 4/7 phase is stable against additional ³He atoms up to 20% and they are promoted into the third layer. We found evidence that such promoted atoms form a self-bound 2D Fermi liquid with an approximate density of 1 nm^?2 from the measured density dependence of the γ-coefficient of heat capacity. We also show evidence for the first-order transition between the commensurate 4/7 phase and the ferromagnetic incommensurate phase in the second layer in the density range of 8.1≤ρ≤9.5 nm^?2.     

Faster Electron Injection and More Active Sites for Efficient Photocatalytic H2 Evolution in g‐C3N4/MoS2 Hybrid

Herein, the structural effect of MoS₂ as a cocatalyst of photocatalytic H₂ generation activity of g‐C₃N₄ under visible light irradiation is studied. By using single‐particle photoluminescence (PL) and femtosecond time‐resolved transient absorption spectroscopies, charge transfer kinetics between g‐C₃N₄ and two kinds of nanostructured MoS₂ (nanodot and monolayer) are systematically investigated. Single‐particle PL results show the emission of g‐C₃N₄ is quenched by MoS₂ nanodots more effectively than MoS₂ monolayers. Electron injection rate and efficiency of g‐C₃N₄/MoS₂‐nanodot hybrid are calculated to be 5.96 × 10⁹ s^?1 and 73.3%, respectively, from transient absorption spectral measurement, which are 4.8 times faster and 2.0 times higher than those of g‐C₃N₄/MoS₂‐monolayer hybrid. Stronger intimate junction between MoS₂ nanodots and g‐C₃N₄ is suggested to be responsible for faster and more efficient electron injection. In addition, more unsaturated terminal sulfur atoms can serve as the active site in MoS₂ nanodot compared with MoS₂ monolayer. Therefore, g‐C₃N₄/MoS₂ nanodot exhibits a 7.9 times higher photocatalytic activity for H₂ evolution (660 µmol g?¹ h^?1) than g‐C₃N₄/MoS₂ monolayer (83.8 µmol g^?1 h^?1). This work provides deep insight into charge transfer between g‐C₃N₄ and nanostructured MoS₂ cocatalysts, which can open a new avenue for more rationally designing MoS₂‐based catalysts for H₂ evolution.     

Absorption Spectrum of Na Atoms Attached to Helium Nanodroplets

We present an analysis of the electronic 3p←3s excitation of Na atoms attached to ³He and ⁴He droplets. Once the ground state structure of the doped drops has been obtained within finite-range density functional theory, we determine the time-correlation function of the Na atom evolving in the full three-dimensional ²Π_1/2, ²Π_3/2 and ²Σ_1/2 potentials generated by its pairwise interaction with the helium atoms. The Fourier analysis of the time-correlation function determines the absorption spectrum of Na, which is compared with the experimental spectrum. We show that the existence of a redshifted shoulder in the absorption line of Na@⁴He _N , absent in Na@³He _N , is due to the wider vibrational motion of the dopant atom in the dimple it causes on the surface of the droplet.     

Finite Size Effects in Adsorption of Helium Mixtures by Alkali Substrates

We investigate the behavior of mixed ³He–⁴He droplets on alkali surfaces at zero temperature, within the frame of Finite Range Density Functional theory. The properties of one single ³He atom on $^4 He_{N_4 }$ droplets on different alkali surfaces are addressed, and the energetics and structure of $^4 He_{N_4 } + ^3 He_{N_3 }$ systems on Cs surfaces, for nanoscopic ⁴He drops, are analyzed through the solutions of the mean field equations for varying number N ₃ of ³He atoms. We discuss the size effects on the single particle spectrum of ³He atoms and on the shapes of both helium distributions.     

Adsorption of 4He N and 4He N 3He Clusters on Cesium

The ground-state properties of helium clusters ⁴He _N and ⁴He _N ³He, for N≤ 40, adsorbed on the surface of cesium are studied using variational and diffusion Monte Carlo calculations. Binding properties are determined using two different Cs–He interaction potentials. For the smallest clusters, self-binding on a Cs surface is stronger than in two or three dimensions. For N > 10 self-binding in three dimensions is stronger than on Cs for both types of Cs–He interaction potential considered. The obtained binding energies and structure are compared to results of recent density functional calculations. The emergence of edge states of ³He atom, localized along the contact line of ⁴He cluster with a cesium surface, is studied. First indication that ³He atom prefers to be close to the contact line appears already for the ⁴He₃ ³He cluster.     

Helium adsorption on exfoliated graphite

High precision adsorption isotherms of³He and⁴He on bare Grafoil and on Grafoil coated with a monolayer of argon have been measured in the temperature range 4–20 K, using a high resolution, pressure-sensitive capacitance gauge located at 4.2 K close to the sample chamber. This gauge obviated thermomolecular pressure effects and corrections. The isotherms yielded the following resultant data: The monolayer coverage V_m for⁴He on bare Grafoil was 0.42 cm³ (STP)/m² and for³He on bare Grafoil was 0.395 cm³ (STP)/m²: the isosteric heat of adsorptionQ _st/R of the second layer of³He on bare Grafoil was 23.5 K andQ _st/R for³He on argon-coated Grafoil for the first layers was 47.5 K. Also, the data for³He and⁴He on bare Grafoil at and just aboveV _m have been used by Novaco (see subsequent paper) for determination of the virial coefficients of the gas phase occuring in the early formation of the second layer.     

The Phase of Submonolayer 4He Films Near Monolayer Completion

We study the state of ⁴He films physisorbed to general Lennard–Jones type substrates at coverages near monolayer completion as a function of the range C₃ and well-depth D of the substrate-helium potential. By examining the liquid-state energetics as well as the coverage dependence of the third sound speed and roton energies in the two-parameter space (C₃,D), we can estimate the position of the boundary between those strongly interacting substrates wherein the ⁴He film essentially forms a quasi two-dimensional solid prior to second layer formation and weaker interacting substrates for which the ⁴He film remains mobile and superfluid. Our approach utilizes a combination of information from both variational calculations and also correlated basis function theory to examine in detail the excitation structure in the monolayer liquid as a function of film coverage and substrate potential.      

Large Mass Enhancement in 3He Monolayer Fluids Adsorbed on Graphite Preplated with 4He

A fluid monolayer of ³He adsorbed on a graphite surface is an ideal twodimensional (2D) Fermi system. We have observed very large mass enhancement of the quasiparticles (m*/m=20±5) in preliminary heat-capacity measurements for high density ³He fluids adsorbed on graphite preplated with a ⁴He monolayer (³He/⁴He/gr). This could be divergence of m* toward the critical density for the 4/7 phase with a triangular lattice, which is a registered phase commensurate against the first layer. The observed m* is larger than those reported for other 2D ³He systems, e.g., m*/m=13 for ³He/HD/HD/gr system, presumably because of the higher critical density. The apparent divergence of m* toward the different Critical densities strongly suggests the Mott–Hubbard type transition between the 2D Fermi fluid phase and the registered phase under a strong onsite hard core repulsion between the 3He atoms.     

Sorption studies of helium and neon by crystals of C60 and C70

We present sorption measurements for³He and⁴He in the temperature range of 1.5 K to 4.1 K, and for²⁰Ne in the temperature range of 22 K to 27 K by crystals of C₆₀, C₇₀ and crystals of the mixture of these two molecules, 80% C₆₀, 20% C₇₀ We analyze these data by taking into account the non-ideality of the gas in equilibrium with the adsorbate. We calculate chemical potentials and isosteric heats. We find that there is no obvious evidence of intercalation of helium in these crystals at low temperatures. At higher temperatures there are some anomalies in the helium isotherms, and indication of excess sorption. The isosteric heat shows a minimum in this region which can be interpreted as penetration of the helium into a region of repulsive potential. We also find that levels of sorption, at the same chemical potential difference from saturation, are higher for⁴He than for³He. They are also higher for⁴He on C₇₀ than for the other crystals. For neon our work is concentrated around the triple point. We find that the isotherms indicate the formation of liquid or solid films. Below the triple point, and above a few atomic layers, the neon film does not grow uniformly.     

Stabilization of High Concentrations of Nitrogen Atoms in Impurity-Helium Solids

Impurity-helium (Im-He) solids created by injecting gaseous helium with an admixture of nitrogen atoms and molecules into superfluid ⁴He have been studied via electron spin resonance (ESR). We have studied the efficiency of stabilization of N atoms in Im-He samples prepared from nitrogen-helium gas mixtures with different fractions of nitrogen varying from 0.25% to 4%. Some of the observed ESR spectra of N atoms in the Im-He samples are very broad. The highest local concentration of N atoms determined from dipole-dipole broadening of the ESR line is ～8×10²⁰ cm^?3. The highest average concentrations of N atoms in N-N2-He solids were much lower (of order 10¹⁹ cm^?3). The samples with high concentrations of N atoms were stable in liquid helium, and remained stable even after draining liquid helium from the sample at T≤3.5 K.     

Superfluidity of 4He Confined in a Porous Glass and Control of the Pore Size

⁴He confined in nanoporous media is one of the most interesting nano-sized systems. The aim of the present work is control of the pore size of nanoporous media in order to clarify the superfluid size effects. For the pore size control, monolayer adsorption of Kr on the pore wall is performed. The change in the pore size distribution by the monolayer adsorption are characterized by N₂ isotherms at 77 K. Superfluidity in the pores is observed with a torsional oscillator method. The pore diameter of the as-purchased Gelsil is estimated at 5.8 nm. The monolayer adsorption reduces the size by 1.1 nm, caused by the thickness of the Kr monolayer. The decrease in the pore size lowers the superfluid transition temperature by 40 mK.     

3He impurities on the bulk surface of liquid4He: Possible existence of excited states

We study, using a density-functional approach, the properties of the two-dimensional system formed by³He atoms on the surface of liquid⁴He, as a function of³He coverageN _s , at zero temperature. We find several types of surface states accessible to the³He atoms. For small values ofN _s , the surface tension is, as expected, linear inN _s ² . For a coverage of about half a monolayer, a new type of surface state starts being occupied, and this produces a change in the slope of as a function ofN _s ² and, more clearly, a step in the surface specific heat, which increases by a factor of almost two. Another step is predicted to occur for a coverage of 1.3 monolayer. Existing data are compatible with this structure of surface states but are not numerous enough to prove or disprove the existence of steps.Unité de Recherche des Universités Paris 11 et Paris 6 Associée au CNRS.     

Sub-boundaries in3He and4He single crystal and their migration below 1K observed by X-ray topography

The observation of alterations in crystal structure at ultra-low temperatures by X-ray diffraction, made possible by the realization of synchrotron radiation use after a quarter of this century, plays an important role in obtaining an understanding of the base structure of solids. For that, two types of³He-⁴He dilution refrigerators with a modified version of the top-loading facilities were installed at the BL-3C₂ and 6C₁ stations of the Photon Factory. In BL-3C₂, the behaviors of lattice defects in solid helium have been studied by X-ray topography. In this note, the migrations of sub-boundaries in³He and⁴He single-crystals are reported as being the result of an annealing effect. After annealing hcp⁴He single crystals for 80min at 0.5K, no change in crystallographic orientations could be easily observed from white SR X-ray topographs. In the same type topographs of bcc³He single crystals after annealing for several hours at 03K, migration of sub-boundaries were conspicuously discerned.     

Specific heat of para-hydrogen monolayers on graphite

The specific heat of para-hydrogen films has been measured from 1 to 20 K for areal densities between 0.01 and 0.055 atoms/Å ² of the partial monolayer adsorbed on grafoil. The results are compared with the specific heat of ⁴ He films at equivalent densities. It is argued that a nonideal gas regime and liquefaction are present in both systems and that solidification of thep-H ₂ films has been suppressed to below the temperature range of the experiment. Implications regarding 2D superfluidity in hydrogen monolayers are discussed briefly.     

Specific heat and Curie temperature evaluation on triangular lattice: Exchange frequencies for3He adsorbed on grafoil,evaluated by path integral techniques

We compute, using path integrals, the cyclic-exchange frequencies of a monolayer of 3 He adsorbed on graphite in the incommensurate solid phase. Interactions between helium atoms are treated with the Aziz potential; between an helium atom and the plan of graphite we use an interaction potential which depends only on the distance above the surface. The specific heat (C _V ) and the magnetic susceptibility () are evaluated from the calculated multiple-exchange hamiltonian. TheC _V value converges with the 2-, 3- and 4-body exchange cycles while larger cycles are needed for the convergence of the value. For the density 0.0785 atom/Ų, we find that the variations ofC _V is antiferromagnetic, whereas the variations of is ferromagnetic.     

Thermal Decomposition Mechanism of N2-Impurity Helium Solids

The mechanism for the thermal decomposition of N₂ containing impurity helium solids (IHS) in superfluid ⁴He is reported. We show that the solid undergoes rapid thermal annealing leading to mobilization of the nitrogen atoms. Subsequently, the nitrogen atoms form molecular N₂ excimers, which are mobile in the solid and are responsible for various emission bands observed over the thermal decomposition of IHS. The present interpretation of the spectroscopic results indicates that IHS contains only ground state atomic species.PACS numbers: 33.20 Kf, 33.70 Jg