Linear and non-linear response of embedded Na clusters

We investigate Na clusters embedded in Ar matrices. The surrounding Ar atoms are modeled in terms of their dynamical polarizability and the strong electron repulsion. The calibration of the model is discussed. First results for the non-linear optical response of the Na clusters are presented for the test case of Na₈ embedded in Ar ensembles of different sizes. It is shown that blue shift through core repulsion and red shift through dipole polarizability counterweight each other to the end that very little global shift is seen in the spectra. This feature persists to all excitation strengths considered. There are, however, detailed effects, such as for example the Landau fragmentation of the Mie plasmon peak. PACS 36.40.Gk; 36.40.Vz; 31.15.Ew     

Electronic excitation processes in rare gas clusters studied by electron energy loss spectroscopy

We present the electron energy loss spectra for Ar clusters as a function of incident electron energy and of cluster size. In spectra measured with 100 eV incident electron energy the bulk excitation peak becomes visible for a mean cluster size above 170 atoms per cluster. For 250 eV incident electron energy the bulk excitation peak is clearly observable even for a mean cluster size of 120 atoms per cluster. These experimental results are qualitatively reproduced by a simple calculation that accounts for the mean free path of electrons in Ar clusters; i.e., the penetration depth of incident electrons into the cluster.     

QCT-based vibrational collisional models applied to nonequilibrium nozzle flows

We investigate from a theoretical perspective structure and dynamics of Na clusters on a surface built from Ar layers grown on a metal support. The system is modeled by a hierarchical quantum-mechanical/molecular-mechanical (QM/MM) approach treating the cluster electrons with time-dependent density-functional theory, the Ar atoms classically, and the metal support as a continuous dielectric medium. Caution has been taken to describe properly the dynamical polarizability of the Ar substrate. We study the effect of the Ar substrate and particularly of the metal support on the cluster structure and dynamics. The binding of Na₆ and Na₈ to the Ar surface is found to by very weak and the effect of the dielectric response of the metal (DRM) turns out to be negligible. The global properties of the optical response of the Na clusters are slightly changed by the Ar substrate and the DRM while the detailed spectral fragmentation depends sensitively on any change of the environment. The deposition dynamics of small Na clusters is crucially influenced by the mechanical hardness of the metal support while the DRM makes little effect. We also study the dependence on the number of Ar layers. For the first few layers (from two to four), the deposition dynamics changes dramatically with the number of layers. The results stabilize from six layers on upwards.     

Dynamics of cluster deposition on Ar surface

Using a combined quantum mechanical/classical method, we study the dynamics of deposition of small Na clusters on Ar(001) surface. We work out basic mechanisms by systematic variation of substrate activity, impact energy, cluster orientations, cluster sizes, and charges. The soft Ar material is found to serve as an extremely efficient shock absorber which provides cluster capture in a broad range of impact energies. Reflection is only observed in combination with destruction of the substrate. The kinetic energy of the impinging cluster is rapidly transfered at first impact. The distribution of the collision energy over the substrate proceeds very fast with velocity of sound. The full thermalization of ionic and atomic energies goes at a much slower pace with times of several ps. Charged clusters are found to have a much stronger interface interaction and thus get in significantly closer contact with the surface.     

碱金属团簇Na2在重离子作用下的离化

在时间相关的局域密度近似理论框架下研究了重离子Ar8+ 和碱金属团簇Na2 随时间演化的相互作用 .给出了电子系统的总能量 ,产生Na2 的各种电荷态的几率和Na2 价电子的平均逃逸数等物理量随时间的演化 ,进而得到了Na2 的离化几率 .在快重离子与团簇作用中 ,可以得到低激发态的团簇离子. Based on the Time Dependent Local Density Approximation(TDLDA), the processes of excitation of sodium clusters by highly charged Ar 8+ions are simulated. The time-dependent probabilities of escaped electrons are obtained, furthermore, the ionization probabilities of the Na 2clusters are deduced.In fast ion-cluster collisions, Na 2cluster ions can be produced with minimum or even no excitation of the cluster itself     

Coupled plasmon and phonon dynamics in embedded Na clusters

We investigate, from a theoretical perspective, the coupled electronic and ionic/atomic dynamics of Na clusters embedded in Ar matrices. The system is described by time-dependent density-functional theory for cluster electrons and classical motion for Na⁺ ions as well as for Ar atoms. The interaction with the surrounding Ar atoms is modelled by polarization potentials plus core repulsion. We use this model to study coupled electronic and ionic/atomic motion in embedded clusters following a very short laser pulse. For excitations in the non-linear regime, we find clear signs for the coherent coupling of the Mie plasmon resonance with ionic vibrations (phonons). In addition, an incoherent line stretching is observed which can be traced back to the turning point of ionic vibrations. The coupling to the atomic motion of the surroundings leads to a slow and far reaching rearrangement of the matrix. PACS 36.40.Gk; 36.40.Vz; 31.15.EW     

Electronic and geometric structure of doped rare-gas clusters: surface, site and size effects studied with luminescence spectroscopy

The electronic and geometric structure of rare gas clusters doped with rare-gas atoms Rg = Xe, Kr or Ar is investigated with fluorescence excitation spectroscopy in the VUV spectral range. Several absorption bands are observed in the region of the first electronic excitations of the impurity atoms, which are related to the lowest spin-orbit split atomic ³P₁ and ¹P₁ states. Due to influence of surrounding atoms of the cluster, the atomic lines are shifted to the blue and broadened (“electronical cage effect”). From the known interaction potentials and the measured spectral shifts the coordination of the impurity atom in Ar_N, Kr_N, Ne_N and He_N could be studied in great detail. In the interior of Kr_N and Ar_N the Xe atoms are located in substitutional sites with 12 nearest neighbours and internuclear distances comparable to that of the host matrix. In Ne_N and He_N the cluster atoms (18 and 22, respectively) arrange themselves around the Xe impurity with a bondlength comparable to that of the heteronuclear dimer. The results confirm that He clusters are liquid while Ne clusters are solid for N≥ 300. Smaller Ne clusters exhibit a liquid like behaviour. When doping is strong, small Rg_m-clusters (Rg = Xe, Kr, Ar, m≤10 ²) are formed in the interior sites of the host cluster made of Ne or He. Specific electronically excited states, assigned to interface excitons are observed. Their absorption bands appear and shift towards lower energy when the cluster size m increases, according to the Frenkel exciton model. The characteristic bulk excitons appear in the spectra, only when the cluster radius exceeds the penetration depth of the interface exciton, which can be considerably larger than that in free Rg_m clusters. This effect is sensitive to electron affinities of the guest and the host cluster.     

Cold Ar 3 + generated by ionization of argon clusters in large helium clusters: Temperature dependence of the photofragmentation

Ionized argon clusters were generated by electron impact ionization of neutral argon clusters embedded in large neutral helium clusters. Photofragmentation spectroscopy of Ar ₃ ⁺ and Ar ₃ ⁺ He produced in this way demonstrates the strong influence of vibrational excitation on the photodissociation dynamics, and indicates the low internal energy of the latter cluster.     

An investigation of the internal temperature dependence of Pd-Pt cluster beam deposition: A molecular dynamics study

We investigated the internal temperature dependence of the Pd_1−aPt_a cluster beam deposition in the present study via the molecular dynamics simulations of soft-landing. By analysis of the velocity distribution and diffusion coefficient of the bimetallic cluster, Pd atoms with better mobility improved the diffusibility of Pt atoms. The radial composition distribution showed that a Pt-core/Pd-shell structure of the cluster formed at high internal temperatures through migrations of the Pd atoms from inner to surface shells. In the soft-landing process, the diffusing and epitaxial behaviors of the deposited clusters mainly depended on the internal temperature because the incident energy of the cluster was very small. By depositing clusters at high internal temperatures, we obtained a thin film of good epitaxial growth as the energetic cluster impact. Furthermore, nonepitaxial configurations such as scattered nonepitaxial atoms, misoriented particles, and grain boundaries of (1 1 1) planes were produced in the growth of the cluster-assembled film. As the size of the incident cluster increased, the internal temperature of the cluster needed for better interfacial diffusion and contact epitaxy on the substrate also rose.     

Ar?NO团簇的同步辐射光电离研究

利用国家同步辐射实验室合肥光源的真空紫外同步辐射，使NO分子和Ar原子混合物的超声分子束发生光电离，测量了Ar，NO和异类团簇Ar·NO的光电离效率谱. 在谱中，在与Ar原子的共振线对应的能量区域(11.5—12.0 eV)观察到一个强的类共振结构. 这个结果表明，在异类团簇Ar·NO的内部，稀有气体Ar原子的激发能转移到与它接触的分子NO上，使分子NO发生电离. 关键词： Ar·NO团簇 同步辐射 光电离 能量转移     

Hindered Coulomb explosion of embedded Na clusters — stopping,shape dynamics and energy transport

We investigate the dynamical evolution of a Na₈ cluster embedded in Ar matrices of various sizes from N=30 to 1048. The system is excited by an intense short laser pulse leading to high ionization stages.We analyze the subsequent highly non-linear motion of cluster and Ar environment in terms of trajectories, shapes, and energy flow. The most prominent effects are: temporary stabilization of high charge states for several ps, sudden stopping of the Coulomb explosion of the embedded Na₈ clusters associated with an extremely fast energy transfer to the Ar matrix, fast distribution of energy throughout the Ar layers by a sound wave. Other ionic-atomic transfer and relaxation processes proceed at slower scale of few ps. The electron cloud is almost thermally decoupled from ions and thermalizes far beyond the ps scale.     

Anisotropic explosions of hydrogen clusters under intense femtosecond laser irradiation

We report on measurements of ion energy distributions from hydrogen clusters irradiated by intense laser pulses of duration 40 and 250 fs. Contrary to the predictions of a simple Coulomb explosion model, we observe a pronounced spatial anisotropy of the ion energies from these explosions with the highest energy ions ejected along the laser polarization direction. The origin of the anisotropy is distinct from that previously seen in clusters of high Z atoms such as Ar and Xe. Furthermore, a measured increase in H+ ion energy when longer, lower intensity pulses are employed suggests that multiple-pass, vacuum heating of the cluster electrons is important in the deposition of energy by the laser.     

Probing the structural,electronic and magnetic properties of small Au4M (M = Sc–Zn) clusters

Density-functional method PW91 has been selected to investigate the structural, electronic and magnetic properties of Au₄M (M =Sc–Zn) clusters. Geometry optimisations show that the M atoms in the ground-state Au₄M clusters favour the most highly coordinated position. The ground-state Au₄M clusters possess a solid structure for M = Sc and Ti and a planar structure for M = V–Zn. The characteristic frequency of the doped clusters is much greater than that of pure gold cluster. The relative stability and chemical activity are analysed by means of the averaged binding energy and highest occupied molecular orbital and lowest unoccupied molecular orbital energy gap for the lowest energy Au₄M clusters. It is found that the dopant atoms can enhance the thermal stability of the host cluster except for Zn atom. The Au₄Ti, Au₄Mn and Au₄Zn clusters have relatively higher chemical stability. The vertical detachment energy, electron affinity and photoelectron spectrum are calculated and simulated theoretically for all the ground-state structures. The magnetism calculations reveal that the total magnetic moment of Au₄M cluster is mainly localised on the M atom and vary from 0 to 5 μ_B by substituting an Au atom in Au₅ cluster with different transition-metal atoms.     

The geometric structure of pure SF6 and mixed Ar/SF6 clusters investigated by core level photoelectron spectroscopy

The S 2p core level photoelectron spectra of Sulphurhexafluoride clusters have been investigated together with heterogeneous Ar/SF₆ clusters, created by doping Ar host clusters (with a mean size of 3600 atoms) with the molecule. Surface and bulk features are resolved both in the argon 2p and the sulphur 2p core level photoelectron spectra. For the latter level such features were only observed in the pure cluster case; a single feature characterizes the S 2p core level spectra of SF₆ doped argon clusters. From the chemical shifts, investigated with respect to SF₆ doping pressure. It can be concluded that the host clusters get smaller with increasing doping pressures and that the SF₆ molecules predominantly stay below the cluster surface, whereas the Argon core stays intact. We have neither observed features corresponding to SF₆ on the cluster surface, nor features corresponding to molecules deep inside the bulk in any of the spectra from the pick-up experiments.     

First evidence for vibrational excitations of large atomic clusters in amorphous semiconductors

Raman and depolarization spectra of GeSe₂ alloyed with Se or As₂Se reveal a sharp vibrational doublet, only one component of which can be attributed to a vibrational excitation of the GeSe₂ local atomic cluster. The composition dependence of the intensity and polarization of the second feature identify it as an excitation involving a substantially larger cluster with high symmetry. The large cluster is a ring of Ge atoms inter-connected through single Se atoms     

The ground state of graphene and graphene disordered by vacancies

Graphene clusters consisting of 24–150 carbon atoms and hydrogen termination at the zigzag boundary edges have been studied, as well as clusters disordered by vacancy(s). Density Function Theory and Gaussian03 software were used to calculate graphene relative stability, desorption energy, band gap, density of states, surface shape, dipole momentum and electrical polarization of all clusters by applying the hybrid exchange-correlation functional Beke–Lee–Yang–Parr. Furthermore, infrared frequencies were calculated for two of them. Different basis sets, 6–31g**, 6–31g* and 6–31g, depending on the sizes of clusters are considered to compromise the effect of this selection on the calculated results. We found that relative stability and the gap decreases according to the size increase of the graphene cluster. Mulliken charge variation increases with the size. For about 500 carbon atoms, a zero HOMO–LUMO gap amount is predicted. Vacancy generally reduces the stability and having vacancy affects the stability differently according to the location of vacancies. Surface geometry of each cluster depends on the number of vacancies and their locations. The energy gap changes as with the location of vacancies in each cluster. The dipole momentum is dependent on the location of vacancies with respect to one another. The carbon–carbon length changes according to each covalence band distance from the boundary and vacancies. Two basis sets, 6-31g* and 6-31g**, predict equal amount for energy, gap and surface structure, but charge distribution results are completely different.     

Structures of Pt clusters on graphene by first-principles calculations

The interactions between Pt_n clusters (n?13) and a graphene sheet have been investigated by first-principles calculations based on density functional theory. For single Pt-atom and Pt₂-dimer adsorptions, the stable adsorption sites are bridge sites between neighboring carbon atoms. When the number of Pt atoms in a cluster increases, the Pt-C interaction energy per contacting Pt atom becomes smaller. For smaller clusters (3?n?7), the adsorption as a vertical planar cluster is more stable than that as parallel planar or three-dimensional (3D) clusters, due to the stability of a planar configuration itself and the stronger planar-edge/graphene interaction, while the adsorption as a parallel planer cluster becomes stable for larger cluster (n?7) via the deformation of the planar configuration so as to attain the planar-edge/graphene contact. For much larger clusters (n?10), the adsorption as a 3D cluster becomes the most stable due to the stability of the 3D configuration itself as well as substantial Pt-C interactions of edge or corner Pt atoms. The interfacial interaction between a Pt cluster and graphene seriously depends on the shape and size of a cluster and the manner of contact on a graphene sheet.     

Structures and electronic properties of M@Au<Subscript>6</Subscript> (M=Al,Si, P,S, Cl,Ar) clusters: a density functional theory investigation

The geometries and electronic properties of the 3p electrons atoms doped gold cluster: M@Au₆ clusters (M=Al, Si, P, S, Cl, Ar) have been systematically investigated by using relativistic all-electron density functional theory (VPSR) and scalar relativistic effective core potential Stuttgart/Dresden (SDD) basis. Generalized gradient approximation in the Perdue-Burke-Ernzerhof (PBE) functional form is chosen for geometry optimization. A number of new isomers are obtained for neutral M@Au₆ clusters. Both PBE/VPSR and PBE/SDD methods give similar lowest energy structure of each M@Au₆cluster. With the exception of Ar@Au₆, all doped clusters show larger relative binding energies compared with pure Au₇ cluster. It is found that all the ground-state structures of the M@Au₆ clusters prefer the low symmetry structures, which is very different to the 3d transition-metal impurity doped Au₆ clusters. Our results are in excellent agreement with available experiment data.