Theory for the short-time response of small Hg n clusters after excitation

The short-time behavior of small Hg _n clusters immediately after single or double ionization is studied. We calculate self-consistently the ground state electronic energyE of ionized Hg _n clusters. Upon ionization changes of the potential energy surface (PES) occur, which govern the atomic motion in the cluster. These changes depend on cluster size and charge and are determined by the interplay between the localization of the holes within an ionic core and the polarization energy of the neutral rest of the cluster. In the case of single ionization of the cluster the PES results mainly from hole delocalization. In contrast, in the case of double ionization the PES is governed almost only by strong environment polarization. We use our theory to explain the physical origin of the oscillations in the ionization cross-section of singly and doubly excited Hg _n clusters observed in recent pump-probe experiments.     

Evolution of bulk-like properties in mercury microclusters

The transition from non-metallic to metallic behavior of mercury microclusters, Hg _n , withn ranging from 2 to 79, is investigated using first principles tight-binding linear muffin-tin orbital method. Then dependence of the ionization potential, the cohesive energy, the energy gap, and the nature of the bonding indicates metallic behavior for Hg _n withn≧80. The average bond length of Hg clusters is found to be larger than that of the bulk. Our results are in good agreement with experiments.     

Calculation of the electronic properties of neutral and ionized divalent-metal clusters

The electronic properties of neutral and ionized divalent-metal clusters have been studied using a microscopic theory, which takes into account the interplay between van der Waals (vdW) and covalent bonding in the neutral clusters, and the competition between hole delocalization and polarization energy in the ionized clusters. By calculating the ground-state energies of neutral and ionized Hg _n clusters, we determine the size dependence of the bond character and the ionization potentialI _p (n). For neutral Hg _n clusters we obtain a transition from van der Waals to covalent behaviour at the critical sizen _c ～10–20 atoms. Results forI _p (Hg _n ) withn≤20 are in good agreement with experiments, and suggest that small Hg _n ⁺ clusters can be viewed as consisting of a positive trimer core Hg ₃ ⁺ surrounded byn?3 polarized neutral atoms.     

Multiple ionization and Coulomb explosion of mercury clusters in femtosecond laser fields

We report on studies of multiple ionization and fragmentation of free Hg_n (n ≤ 80) clusters in the femtosecond time domain at wavelengths ranging from 255 nm to 800 nm. After excitation by single laser pulses of an intensity of 5 * 10¹¹ W/cm² we observe prompt formation of multiply charged Hg_n clusters. The Hg_n cluster size distribution observed up to n ≈ 80 shows in additon to singly charged also doubly and triply charged clusters with a surprisingly high amount of doubly charged clusters. The measured cluster size distribution is nearly independent of laser wavelengths. For higher laser intensities (2 * 10¹² W/cm²) we observe multiply charged mercury atoms up to Hg⁵⁺. At 10¹³ W/cm² molecules and clusters eventually disappear due to Coulomb explosion and complete Fragmentation. Only atomic ions, singly and multiply charged, with high kinetic energies are then observed.     

A REMPI study of solvation of small Hg n clusters by polar molecules

Free Hg _n (DME) _m clusters (where DME=dimethyl-ether,n=1, 2, 3,m=1÷5) formed in a supersonic expansion were studied by the REMPI (Resonance-Enhanced Multi-Photon Ionization) technique. A large decrease of ionization energies due to solvation of Hg _n clusters is observed. Preliminary results are discussed in terms of different equilibrium configurations of the electronic ground, excited and ionic states of clusters.     

Calculation of the size dependence of the ionization energy and autoionization energy of Hg-clusters

To study the transition from van der Waals to metallic bonding we calculate the size dependence of the ionization energy and 5d→6p autoionization energy of Hg _n -clusters using a parametrized LCAO model. Our results are in good qualitative agreement with experiment. Comparison with experimental results suggests that electron correlations play an important role for the transition from localized (van der Waals-like) to delocalized (covalent or metallic) electronic states occuring in Hg _n atn?13–19.     

Study of the fragmentation of small sulphur clusters

The fragmentation of sulphur clusters caused by electron impact ionization was studied. For this purpose, a beam ofS _n -clusters withn≦8 was generated in a gas aggregation source and ionized by electrons of variable energy. Special care was taken to maintain constant nucleation conditions so that the neutral cluster composition remained unchanged. It was found that the cluster ion mass spectra drastically depend on the electron energy. Even near threshold fragmentation processes contribute significantly to the dependence of the ion intensities on the electron energy.     

Electron impact ionization of silver clusters Ag n,n≦36

Electron impact ionization of gas phase silver clusters Ag _n ,n≦36 has been achieved in the threshold region. The vertical ionization potentials in this region clearly demonstrate the evidence of shell effects as well as a distinct even-odd oscillation up ton?20. Their general size dependence is somewhat different from that of the alkali metal clusters due to the presence of thed-electrons.     

Photocatalytic properties of graphene-supported titania clusters from density-functional theory

Density-functional theory calculations of (TiO₂)_n clusters (n = 1–5) in the gas phase and adsorbed on pristine graphene as well as graphene quantum dots are presented. The cluster adsorption is found to be dominated by van der Waals forces. The electronic structure and in particular the excitation energies of the bare clusters and the TiO₂/graphene composites are found to vary largely in dependence on the size of the respective constituents. This holds in particular for the energy and the spatial localization of the highest occupied and lowest unoccupied molecular orbitals. In addition to a substantial gap narrowing, a pronounced separation of photoexcited electrons and holes is predicted in some instances. This is expected to prolong the lifetime of photoexcited carriers. Altogether, TiO₂/graphene composites are predicted to be promising photocatalysts with improved electronic and photocatalytic properties compared to bulk TiO₂.     

Threshold photoionization behaviour of (Li2O)Lin clusters produced by a laser vaporization source

We report on the production of small and medium size lithium and lithium oxide clusters by a laser vaporization cluster source. The isotopomeric distribution of natural lithium allowed to identify Li_kO clusters as the most abundant components in the mass spectrum. Photoionization efficiency curves of Li_kO clusters with photon energies from 3.4 to 4.7 eV were measured for 8 ≤ k ≤ 27. Using linear extrapolation of the increase in photoionization efficiency with photon energy, ionization potentials were extracted. With the chemical bond of the O^2- anion to two Li atoms, leaving n = k-2 valence electrons in the (Li₂O)Li_n clusters, clear shell closure effects are present at n = 8 and n = 20.     

Ionization dynamics of van-der-Waals clusters

The ionization process of homogeneous and heterogeneous van-der-Waals clusters has been investigated using various ionization methods (electron bombardment, charge exchange, photoionization methods), and different analyzing techniques. Direct and indirect ionization processes can be distinguished in the experiments from the shape of the ionization curve which depends on the type of cluster. These features appear differently in homogeneous and heterogeneous systems: Homogeneous systems exhibit characteristic ionization efficiency curves where the direct ionization path appears as a sudden increase in the ionization efficiency while the indirect transition gives rise to a long drawn out tail extending to the true ionization threshold. In heterogeneous clusters the indirect ionization path proceeds via excited states of the component with the larger ionization potential and subsequent energy transfer to the other component. These transitions are shifted and broadened depending on the type of internal interaction. Conclusions are drawn concerning the geometry and the interaction potential inside the cluster. The resolution of the TEPICO (Threshold Electron Photo Ion Coincidence) experiments makes it possible to determine the kinetic energy release of the fragments. It is shown that the results are related to the stabilities of the cluster ions involved in the fragmentation chain. Results are presented for pure rare gas clusters (Ar _n , Kr _n , Xe _n ) and for mixed systems (Ar _n O_2m , Ar _n Xe, Kr _n Xe, (CH₄) _n Ne).     

Hot tungsten clusters: competition between atom ejection and thermionic emission

This is a first report concerning the thermionic emission of electrons from hot metal clusters. Tungsten clusters were exposed to a 10 ns laser pulse, and the delayed emission of electrons from the clusters was recorded as a function of time after the excitation. A large yield of W _n ⁺ cluster ions, which were born as late as microseconds after the laser pulse, has been detected forn>4. Tungsten cluster ions created via thermionic emission show no measurable metastable decay during the flight time in the mass spectrometer. This indicates that they are colder than expected, if evaporative cooling after prompt ionization would prevail.     

ECP-CI study of electronic structure and geometry of small neutral and charged Ag n clusters; Predictions and interpretation of measured properties

The ground state geometries of small neutral Ag _n (n=2–9) and charged Ag _n ^± (n=2–9) clusters have been determined in the framework of the SCF procedure employing a relativistic pseudopotential accounting for core-valence correlation effects (RECP-CVC). Similarities and differences between neutral and charged clusters have been found. Large scale CI for 5s electrons only has been carried out for determining stabilities, ionization potentials (IP) and vertical detachment energies (VDE) of anions. A comparison between predicted and measured observables allows for the tentative structural assignments. In addition, the low lying energies of excited states for the neutral species at the anionic geometries have been calculated to account fully for geometrical and spectroscopic assignment to the photodetachment measurements.     

Simple metal clusters

The response of alkali cluster ions to an optical excitation is investigated for two different photon energy domains. Below the ionization potential giant resonances in the photoabsorption cross-section are observed for closed shell species. Above the ionization potential, the ionization process competes with the photofragmentation process. The number of valence electrons determines both the behavior of the photoabsorption spectrum and the evolution of the ionization cross-section with the cluster size. The stability of the clusters against an excess of charge is examined through the observation of an asymmetric fission of Na _n ⁺⁺ . Experimental results are discussed in term of an electrostatic model giving an estimate of the critical size of stability and of the height of the coulombic barrier.     

Observation of doubly charged mercury cluster ions Hg n 2+, n=1-10 using secondary ion mass spectrometry

Mass spectra of doubly charged mercury clusters (m/z=30-1065) were investigated by secondary ion mass spectrometry. Positively charged ions were generated from an amalgam of mercury and silver by bombardment with a xenon ion beam and mass analysis by a grand-scale sector type mass spectrometer. Hg _n ²⁺, n=1-10 and Hg _n +, n =1- 5 were observed. Some doubly charged mercury clusters, (Hg _n ²⁺) survived at least for 0.1 ms.     

Electronic properties of aluminum clusters compared with the jellium model

The experimental polarizabilities, ionization potentials and electron affinities of aluminum clusters are compared with jellium predictions. It is found that the clusters have radii and work functions which are close to the jellium model predictions for clusters with more than 13 atoms. The polarizabilities of Al _n correspond with the jellium only forn>40 and the shell structure features in the ionization potentials are anomalous up to 37. We conclude that nonjellium effects are important up ton=40.     

Unimolecular dissociation of trivalent metal cluster ions (Al n + , Ga n + , In n + ): evidence for a transition from covalent to metallic bonding

Unimolecular dissociation of aluminum, gallium and indium clusters is investigated. Small sizes dissociate into two channels: either the evaporation of a neutral or a charged monomer. Above a given size n _c, only dissociation of a neutral atom subsists. The evaporation of a charged monomer is characteristic of trivalent metal clusters and is consistent with the size evolution of the ionization potential towards the atomic value. The experiments are interpreted in the framework of the statistical R.R.K. model. For smaller sizes (n < n _c), as two evaporation processes are in competition, we have evaluated cluster relative dissociation energies and ionization potentials. The competition between the two evaporation channels is well mirrored by the evolution of the ionization potentials independently measured by near-threshold photoionization experiments. For gallium, our measurements have revealed that the covalent to metal transition occurs for larger sizes (n = 30–50 atoms) than for aluminum clusters.     

Interaction behavior study of HCl on (ZnS)n (n = 1–12) clusters and HCl effect on Hg0 adsorption

The interaction behavior of HCl and (ZnS)_n (n = 1–12) clusters and HCl effect on Hg⁰ adsorbed by (ZnS)_n have been studied theoretically. The combined genetic algorithm and density functional theory (GA-DFT) method has been used to obtain the structures of (ZnS)_nHCl and (ZnS)_nHgHCl (n = 1–12) clusters. The structural properties of (ZnS)_nHCl and (ZnS)_nHgHCl have been analyzed. The adsorption energies and interaction energies have been calculated. Bond length and bond order analysis has revealed that S H and Zn Cl bonds form after HCl adsorbed on (ZnS)_n clusters, while Hg⁰ can only weakly bind with (ZnS)_nHCl clusters. According to thermodynamic adsorption analysis, the formation of (ZnS)_nHCl clusters from (ZnS)_n and HCl are spontaneous because of their negative Gibbs free energy changes. The formation of (ZnS)_nHgHCl from (ZnS)_nHCl and Hg are nonspontaneous for n = 1–4 and 9, and the Gibbs free energy changes have small negative values for other sizes. Electron localization function and noncovalent interaction (NCI) analysis of (ZnS)₁₀HgHCl manifest that Hg and its nearest Zn form zinc amalgam. Projected density of state study has been performed to obtain the interaction nature of HCl and (ZnS)_n clusters and Hg⁰ adsorption on (ZnS)_nHCl clusters. Based on our study, HCl is chemical adsorbed by (ZnS)_n clusters except (ZnS)₄ cluster. After (ZnS)_n adsorbs HCl, Hg⁰ can physically adsorb on (ZnS)_nHCl clusters. The strength of Hg⁰ on (ZnS)_nHCl is comparable to that of Hg⁰ on (ZnS)_n, indicating that HCl can hardly affect the adsorption of Hg⁰ on ZnS clusters.     

Photoionization studies of transition metal clusters: Ionization potentials of ScnO (n=5−36)

The photoionization efficiency (PIE) spectra and ionization potentials are reported for scandium cluster monoxides (Sc _n O,n=5–36). As found for other transition metal clusters, strong dependence of ionization potential on cluster size is found for small clusters, with the ionization potentials of larger clusters decreasing relatively smoothly with increasing size. The IPs are 0.6–0.8 eV lower than that predicted by conducting spherical droplet model.Performed at Argonne National Laboratory     

Optical response of small carbon clusters

We apply the time-dependent local density approximation (TDLDA) to calculate dipole excitations in small carbon clusters. A strong low-frequency mode is found which agrees well with observation for clusters C_n with n in the range 7–15. The size dependence of the mode may be understood simply as the classical resonance of electrons in a conducting needle. For a ring geometry, the lowest collective mode occurs at about twice the frequency of the collective mode in the linear chain, and this may also be understood in simple terms.