Doped Clusters Research Articles

Reactivity and Regioselectivity of Aluminum Nanoclusters: Insights from Regional Density Functional Theory

The structure and bonding in charged and doped aluminum clusters have been investigated using Regional Density Functional Theory (RDFT). The RDFT method provides a measure of the electronic stress tensor from which it is possible to determine bond indices and electronic chemical potential. We find that the distribution of bond indices on the surface of Al12X clusters provides not only an understanding of the internal bonding and stability but also some insight into the regioselectivity observed in reactions of the clusters.

Impurities good and bad: Doped cluster nanoplasmas in intense laser fields and characterization of impurity level

Doping of cluster-based targets can bring out considerable modifications in the evolution of the nanoplasma formed from clusters in intense laser fields. The consequence could be either an increase or, a decrease (depending upon the properties and proportion of the dopant) in the emission of the resulting charge particles or photons from nanoplasma. As we can control the percentage of CS2 in the doped Ar-CS2 cluster, we can have argon-doped CS2 cluster (when argon constitutes about 10–40%) and CS2-doped argon cluster (when fraction of CS2 is 10–40%). In the experimental studies of electron spectra and X-ray emission from pristine Arn (n ≤ 25, 000) and doped Ar-CS2 clusters at laser intensities of about 1015 W cm−2, it is observed that there is more than an order of magnitude enhancement in those emissions in doped Ar-CS2 clusters than in the former case. Conversely, a significant reduction in those emissions was found in the latter case. Such observations signify the importance of characterization of these targets. In this direction, we demonstrate a simple method for the characterization of doping level based on the Rayleigh scattering measurements.

Microscopic description of small doped 3He clusters through the full‐configuration‐interaction nuclear orbital approach: The (3He)N‐Br2(X) case revisited

AbstractWe have completed our previous study on small (3He)N‐Br2(X) clusters (de Lara‐Castells et al., J Chem Phys (Communication) 2006, 125, 221101) by using larger one‐particle basis sets and an enhanced implementation of the full‐configuration‐ interaction nuclear orbital treatment to calculate ground and excited “solvent” states of small doped 3HeN clusters (de Lara‐Castells et al., J Chem Phys 2009, 131, 194101). Because of the inherent hard‐core interaction problem owing to the strong He–He repulsive potential at short distances, very large one‐particle basis sets are necessary to get converged results. Very similar results to those found for clusters with Cl2(B) as the dopant species have been found, owing more to the rather similar anisotropic T‐shaped character of the used He‐dopant potential energy surfaces than to the dominance of the He‐dopant attractive interaction over the He–He one in both cases. The results of the numerical testing by modifying the strength of the He–He potential interaction provide further evidences into the microscopic interactions holding the clusters together. © 2010 Wiley Periodicals, Inc. Int J Quantum Chem, 2011

Disparate Effects of Cu and V on Structures of Exohedral Transition Metal-Doped Silicon Clusters: A Combined Far-Infrared Spectroscopic and Computational Study

The growth mechanisms of small cationic silicon clusters containing up to 11 Si atoms, exohedrally doped by V and Cu atoms, are described. We find that as dopants, V and Cu follow two different paths: while V prefers substitution of a silicon atom in a highly coordinated position of the cationic bare silicon clusters, Cu favors adsorption to the neutral or cationic bare clusters in a lower coordination site. The different behavior of the two transition metals becomes evident in the structures of Si(n)M(+) (n = 4-11 for M = V, and n = 6-11 for M = Cu), which are investigated by density functional theory and, for several sizes, confirmed by comparison with their experimental vibrational spectra. The spectra are measured on the corresponding Si(n)M(+)·Ar complexes, which can be formed for the exohedrally doped silicon clusters. The comparison between experimental and calculated spectra indicates that the BP86 functional is suitable to predict far-infrared spectra of these clusters. In most cases, the calculated infrared spectrum of the lowest-lying isomer fits well with the experiment, even when various isomers and different electronic states are close in energy. However, in a few cases, namely Si(9)Cu(+), Si(11)Cu(+), and Si(10)V(+), the experimentally verified isomers are not the lowest in energy according to the density functional theory calculations, but their structures still follow the described growth mechanism. The different growth patterns of the two series of doped Si clusters reflect the role of the transition metal's 3d orbitals in the binding of the dopant atoms.

The applicability of three-dimensional aromaticity in BiSnn− Zintl analogues

Three-dimensional aromaticity is shown to play a role in the stability of deltahedral Zintl clusters and here we examine the connection between aromaticity and stability. In order to gain further insight, we have studied Zintl analogs comprised of bismuth doped tin clusters with photoelectron spectroscopy and theoretical methods. To assign aromaticity, we examine the ring currents induced around the cage by using the nucleus independent chemical shift. In the current study, BiSn(4)(-) is a stable cluster and fits aromatic criteria, while BiSn(5)(-) is found to fit antiaromatic criteria and has reduced stability. The more stable clusters exhibit an aromatic character which originates from weakly interacting s-states and bonding orbitals parallel to the surface of the cluster, while nonbonding lone pairs perpendicular to the surface of the cluster account for antiaromaticity and reduced stability. The effect of three-dimensional aromaticity on the electronic structure does not result in degeneracies, so the resulting variations in stability are smaller than those seen in conventional aromaticity.

Clusters in intense FLASH pulses: ultrafast ionization dynamics and electron emission studied with spectroscopic and scattering techniques

FLASH, the first FEL operating at short wavelength, has paved the way for novel types of experiments in many different scientific disciplines. Key questions for the first experiments with this new type of light source are linked to light–matter interaction and ionization processes. This paper gives an overview of the ultrafast ionization dynamics and electron emission of pure and doped rare gas clusters illuminated with intense short-wavelength pulses by summarizing the findings of recent years' work at FLASH. Atomic clusters are ideal for investigating the light–matter interaction because their size can be tuned from the molecular to the bulk regime, thus allowing us to distinguish between intra and interatomic processes. The ionization processes turned out to be strongly wavelength dependent. Plasma absorption, while dominant at 13 eV, becomes insignificant at photon energies above 40 eV. The cluster ionization and disintegration proceed in several steps on a time scale from fs to ps. Insight into the involved processes can be obtained with ion and electron spectroscopy. The high intensity of FLASH pulses opens the door for a new imaging approach to study nanoparticles. Scattering patterns of single and few clusters can be recorded in a single shot. Initial results of scattering experiments and their comparison to Mie calculations show that two- and three-dimensional structural information of gas phase particles can be obtained this way.

Theoretical investigation of ZnO and its doping clusters

Four clusters of ZnO, O-Zn-SR (-SR = ligand) and doping ZnO structures (with Cr, Cu, Al atoms) were investigated using density functional theory at theB3LYP/Lanl2dz level. The characteristics of Zn(3)O(3) and Zn(4)O(4) structures, which are the units of experimental wurtzite and zinc blende structures, were found to be similar to those of experimental ZnO nanocrystals. Moreover, the calculated Raman and IR spectra of ZnO clusters were almost consistent with experimental results. Raman spectra were observed to shift to higher frequencies with decreasing numbers of atoms. Both ligands and solvent make the wavelength of absorption peaks shift to blue. All transitions of absorption peaks for these pure clusters were from d to p orbitals. Finally, doping clusters and experimental doping nanocrystals were similar in character. The doping of metal changed the orbital of ZnO nanocrystals. The transitions in doping clusters (Cr-ZnO, Cu-ZnO) are from d to d orbitals, while Al-ZnO clusters have s-p transitions.

Quantum solvent states and rovibrational spectra of small doped H3e clusters through the full-configuration-interaction nuclear orbital approach: The (H3e)N–Cl2(X) case (N≤4)

A full-configuration-interaction nuclear orbital treatment has been recently developed as a benchmark quantum-chemistry-like method to study small doped (3)He clusters [M. P. de Lara-Castells et al., J. Chem. Phys. 125, 221101 (2006)]. Our objective in this paper is to extend our previous study on ((3)He)(N)-Cl(2)(B) clusters, using an enhanced implementation that allows employing very large one-particle basis sets [M. P. de Lara-Castells et al., J. Chem. Phys. 131, 194101 (2009)], and apply the method to the ((3)He)(N)-Cl(2)(X) case, using both a semiempirical T-shaped and an ab initio He-dopant potential with minima at both T-shaped and linear conformations. Calculations of the ground and low-lying excited solvent states stress the key role played by the anisotropy of the He-dopant interaction in determining the global energies and the structuring of the (3)He atoms around the dopant. Whereas (3)He atoms are localized in a broad belt around the molecular axis in ground-state N-sized complexes with N=1-3, irrespective of using the T-shaped or the ab initio He-dopant potential function, the dopant species becomes fully coated by just four (3)He atoms when the He-dopant potential also has a minimum at linear configurations. However, excited solvent states with a central ring-type clustering of the host molecule are found to be very close in energy with the ground state by using the ab initio potential function. A microscopic analysis of this behavior is provided. Additional simulations of the molecular rovibrational Raman spectra, also including excited solvent states, provide further insights into the importance of proper modeling the anisotropy of the He-dopant interaction in these weakly bound systems and of taking into account the low-lying excitations.

Accurate evaporation rates of pure and doped water clusters in vacuum: A statistico-dynamical approach

Unimolecular evaporation of selected pure (H(2)O)(n) and heterogeneous (H(2)O)(n-1)X(+) water clusters containing a single hydronium or ammonium impurity is investigated in the framework of phase space theory (PST) in its orbiting transition state version. Using the many-body polarizable Kozack-Jordan potential and its extensions for X(+)=H(3)O(+) and NH(4) (+), the thermal evaporation of clusters containing 21 and 50 molecules is simulated at several total energies. Numerous molecular dynamics (MD) trajectories at high internal energies provide estimates of the decay rate constant, as well as the kinetic energy and angular momentum released upon dissociation. Additional Monte Carlo simulations are carried out to determine the anharmonic densities of vibrational states, which combined with suitable forms for the rotational densities of states provide expressions for the energy-resolved differential rates. Successful comparison between the MD results and the independent predictions of PST for the distributions of kinetic energy and angular momentum released shows that the latter statistical approach is quantitative. Using MD data as a reference, the absolute evaporation rates are calculated from PST over broad energy and temperature ranges. Based on these results, the presence of an ionic impurity is generally found to decrease the rate, however the effect is much more significant in the 21-molecule clusters. Our calculations also suggest that due to backbendings in the microcanonical densities of states the variations of the evaporation rates may not be strictly increasing with energy or temperature.

Density functional study of structural and electronic properties of bimetallic copper–gold clusters: comparison with pure and doped gold clusters

The geometrical structures, relative stabilities, and electronic properties of small bare gold clusters Au(n)(lambda) and bimetallic complexes of bare metal clusters with one copper atom Au(n-1)Cu(lambda) (charge lambda = 0, +1, -1; 2 < or = n < or = 9) have been systematically investigated by means of first-principles density functional calculations at the B3LYP level. The results show that the most stable isomers have a planar structure and resemble pure gold clusters in shape, and no three-dimensional isomers were obtained for neutral and anionic doped gold clusters. However, the geometries of Au(n-1)Cu(+) are found to undergo a structural change from two dimensional to three dimensional when the cluster contains 7 atoms. The calculated dissociation energy and second difference energy as a function of the cluster size exhibit a pronounced even-odd alternation phenomenon. Ionization potentials and electron detachment energies (both vertical and adiabatic) of Au(n)(lambda) and Au(n-1)Cu(lambda) clusters are discussed and compared with available experimental results. A good agreement between experimental and theoretical results suggests good prediction of the lowest energy structures for all clusters calculated in the present study.

First principle calculations of yttrium-doped palladium clusters

Abstract Using density-functional methods to study yttrium-doped palladium clusters, Pd n − 1 Y ( n = 2 – 9 ) and Pd n − 2 Y 2 ( n = 3 – 9 ) , different stable geometrical configurations originating from one and two Y-atom substitutions in parent Pdn clusters have been investigated. The calculated fragmentation energies manifest that the two sequences of doped clusters both have enhanced stabilities. All singly-doped isomers have the total magnetic moments of about 1 μ B . For doubly-doped clusters, all isomers are nonmagnetic. Such regularities have not been previously observed to the best of our knowledge. The Y atoms of both doped cluster sequences prefer to occupy sites with the largest coordination number. For all the Y-doped Pd clusters, singly-doped clusters would be applied to use as catalyzers with more possibilities.

Experimental Detection and Theoretical Characterization of Germanium-Doped Lithium Clusters LinGe (n = 1−7)

We report a combined experimental and quantum chemical study of the small neutral and cationic germanium-doped lithium clusters Li(n)Ge(0,+) (n = 1-7). The clusters were detected by time-of-flight mass spectrometry after laser vaporization and ionization. The molecular geometries and electronic structures of the clusters were investigated using quantum chemical calculations at the DFT/B3LYP and CCSD(T) levels with the aug-cc-pVnZ basis sets. While Li3Ge(0,+) and Li4Ge+ prefer planar structures, the clusters from Li4Ge to Li7Ge and the corresponding cations (except Li4Ge+) exhibit nonplanar forms. Clusters having from 4 to 6 valence electrons prefer high spin structures, and low spin ground states are derived for the others because valence electron configurations are formed by filling the electron shells 1s/1p/2s/2p based on Pauli's and Hund's rules. Odd-even alternation is observed for both neutral and cationic clusters. Because of the closed electronic shells, the 8- and 10-electron systems are more stable than the others, and the 8-electron species (Li4Ge, Li5Ge+) are more favored than the 10-electron ones (Li6Ge, Li7Ge+). This behavior for Ge is different from C in their doped Li clusters, which can be attributed to the difference in atomic radii. The averaged binding energy plot for neutrals tends to increase slowly with the increasing number of Li atoms, while the same plot for cations shows a maximum at Li5Ge+, which is in good agreement with the mass spectrometry experiment. Atom-in-molecules (AIM) analysis suggests that Li atoms do not bond to one another but through Ge or pseudoatoms, and an essentially ionic character can be attributed to the cluster chemical bonds. An interesting finding is that the larger clusters have the smallest adiabatic ionization energies known so far (IEa approximately 3.5 eV).

A Hardware-Accelerated Quantum Monte Carlo framework (HAQMC) for N-body systems

Interest in the study of structural and energetic properties of highly quantum clusters, such as inert gas clusters has motivated the development of a hardware-accelerated framework for Quantum Monte Carlo simulations. In the Quantum Monte Carlo method, the properties of a system of atoms, such as the ground-state energies, are averaged over a number of iterations. Our framework is aimed at accelerating the computations in each iteration of the QMC application by offloading the calculation of properties, namely energy and trial wave function, onto reconfigurable hardware. This gives a user the capability to run simulations for a large number of iterations, thereby reducing the statistical uncertainty in the properties, and for larger clusters. This framework is designed to run on the Cray XD1 high performance reconfigurable computing platform, which exploits the coarse-grained parallelism of the processor along with the fine-grained parallelism of the reconfigurable computing devices available in the form of field-programmable gate arrays. In this paper, we illustrate the functioning of the framework, which can be used to calculate the energies for a model cluster of helium atoms. In addition, we present the capabilities of the framework that allow the user to vary the chemical identities of the simulated atoms. Program summary Program title: Hardware Accelerated Quantum Monte Carlo (HAQMC) Catalogue identifier: AEEP_v1_0 Program summary URL: http://cpc.cs.qub.ac.uk/summaries/AEEP_v1_0.html Program obtainable from: CPC Program Library, Queen's University, Belfast, N. Ireland Licensing provisions: Standard CPC licence, http://cpc.cs.qub.ac.uk/licence/licence.html No. of lines in distributed program, including test data, etc.: 691 537 No. of bytes in distributed program, including test data, etc.: 5 031 226 Distribution format: tar.gz Programming language: C/C++ for the QMC application, VHDL and Xilinx 8.1 ISE/EDK tools for FPGA design and development Computer: Cray XD1 consisting of a dual-core, dualprocessor AMD Opteron 2.2 GHz with a Xilinx Virtex-4 (V4LX160) or Xilinx Virtex-II Pro (XC2VP50) FPGA per node. We use the compute node with the Xilinx Virtex-4 FPGA Operating system: Red Hat Enterprise Linux OS Has the code been vectorised or parallelized?: Yes Classification: 6.1 Nature of problem: Quantum Monte Carlo is a practical method to solve the Schrödinger equation for large many-body systems and obtain the ground-state properties of such systems. This method involves the sampling of a number of configurations of atoms and averaging the properties of the configurations over a number of iterations. We are interested in applying the QMC method to obtain the energy and other properties of highly quantum clusters, such as inert gas clusters. Solution method: The proposed framework provides a combined hardware–software approach, in which the QMC simulation is performed on the host processor, with the computationally intensive functions such as energy and trial wave function computations mapped onto the field-programmable gate array (FPGA) logic device attached as a co-processor to the host processor. We perform the QMC simulation for a number of iterations as in the case of our original software QMC approach, to reduce the statistical uncertainty of the results. However, our proposed HAQMC framework accelerates each iteration of the simulation, by significantly reducing the time taken to calculate the ground-state properties of the configurations of atoms, thereby accelerating the overall QMC simulation. We provide a generic interpolation framework that can be extended to study a variety of pure and doped atomic clusters, irrespective of the chemical identities of the atoms. For the FPGA implementation of the properties, we use a two-region approach for accurately computing the properties over the entire domain, employ deep pipelines and fixed-point for all our calculations guaranteeing the accuracy required for our simulation.

Structural, electronic, and magnetic properties of TMZn 11O 12 and TM 2Zn 10O 12 clusters (TM = Sc, Ti, V, Cr, Mn, Fe, Co, Ni, and Cu)

We investigate the structural, electronic and magnetic properties of transition metal (TM = Sc, Ti, V, Cr, Mn, Fe, Co, Ni, and Cu) doped (ZnO) 12 clusters (TMZn 11O 12 and TM 2Zn 10O 12) by using density functional theory approach. All the substitutional doping clusters are of high stability and remain quasi-cage structures with the exception of Ti 2Zn 10O 12 and V 2Zn 10O 12. The doped TMZn 11O 12 clusters are magnetic except TM = Ti, whereas the TM 2Zn 10O 12 clusters are either antiferromagnetic or paramagnetic, suggesting that concentration of TM dopant has great influence on the magnetism of the ZnO-based nanostructures. The magnetic behavior is understood from charge-transfer model and partial density of states.

First‐principles study of molecular hydrogen dissociation on doped Al12X (X = B, Al, C, Si, P, Mg, and Ca) clusters

Inspired by the concept of superatom via substitutionally doping an Al13 magic cluster, we investigated the H2 molecule dissociation on the doped icosahedral Al12X (X = B, Al, C, Si, P, Mg, and Ca) clusters by means of density functional theory. The computed reaction energies and activation barriers show that the concept of superatom is still valid for the catalysis behavior of doped metal clusters. The hydrogen dissociation behavior on metal clusters characterized by the activation barrier and reaction energy can be tuned by controllable doping. Thus, doped Al12X clusters might serve as highly efficient and low-cost catalysts for hydrogen dissociation.

The study of the electronic structures and properties of pure and transition metal-doped silicon nanoclusters: a density functional theory approach

This report presents the study of ab initio electronic structure and properties of pure and transition metal (TM = Ti, Zr and Hf)-doped silicon clusters, TM@Si(n), by using density functional theory with a polarised basis set (LanL2DZ) within the spin-polarised generalised gradient approximation for different values of n varying from 8 to 20. As the first step of the study, different optimised geometries of pure and doped clusters are calculated. These optimised clusters are then used to calculate different structural and physical parameters of the clusters, like binding energy, Highest Occupied Molecular Orbital – Lowest Unoccupied Molecular Orbital (HOMO–LUMO) gap, charge transfer, etc. In order to check the stability of the clusters, the second-order difference in the energy of the optimised structures is calculated. To study the optical behaviour of the clusters, infrared and Raman spectra are also calculated. Further calculations are also done on cation and anion clusters of both pure and doped nanoclusters to obtain their ionisation potential, electron affinity and chemical potential. An effort has been made to correlate the variation of different calculated parameters with the size of the clusters to explain the real existence and stabilities of different TM-doped clusters.

Experimental and theoretical investigation of three-dimensional nitrogen-doped aluminum clusters Al8N− and Al8N

The structure and electronic properties of the Al(8)N(-) and Al(8)N clusters were investigated by combined photoelectron spectroscopy and ab initio studies. Congested photoelectron spectra were observed and experimental evidence was obtained for the presence of multiple isomers for Al(8)N(-). Global minimum searches revealed several structures for Al(8)N(-) with close energies. The calculated vertical detachment energies of the two lowest-lying isomers, which are of C(2v) and C(s) symmetry, respectively, were shown to agree well with the experimental data. Unlike the three-dimensional structures of Al(6)N(-) and Al(7)N(-), in which the dopant N atom has a high coordination number of 6, the dopant N atom in the two low-lying isomers of Al(8)N(-) has a lower coordination number of 4 and 5, respectively. The competition between the Al-Al and Al-N interactions are shown to determine the global minimum structures of the doped aluminum clusters and results in the structural diversity for both Al(8)N(-) and Al(8)N.

Using a Jacobi–Davidson “Nuclear Orbital” Method for Small Doped 3 He Clusters

An efficient full configuration-interaction (CI) treatment has been recently developed as a benchmark quantum chemistry (QC) method to study doped 3HeN clusters [J Chem Phys 125:221101, 2006]. The method, which uses an iterative Jacobi-Davidson diagonalization algorithm, is applied here to small clusters (N ≤ 4) containing Cl2 as dopant.

Theoretical study of the coadsorption of CO and O2 on doped cationic gold clusters MAun + (M = Ti, Fe, Au; n = 1, 6, 7)

We present a study based on first-principles calculations of the adsorption of CO on selected equilibrium configurations of MAu n O 2 + (M = Ti, Fe; n = 1, 6, 7) complexes resulting from the adsorption of O 2 on doped cationic gold clusters MAu n + . Empirical rules for the formation of CO 2 -MAu n O + complexes are outlined. The desorption energy of CO 2 is calculated. The adsorption of a second CO molecule on the residual MAu n O + complex leads in some cases to the formation of CO 2 -MAu n + . The desorption of a second CO 2 molecule brings back to the initial doped gold cluster MAu n + .

Effect of sulphur doping on manganese clusters: an ab initio study

We report a structural, electronic and magnetic analysis of minimal MnnS clusters, n = 1–13, from ab initio calculations. Total geometry optimizations were performed by considering compact manganese clusters, doped with a single sulphur atom. The doping was added to the cluster by considering substitution, interstitial and adsorbed positions. To further investigate the influence of the sulphur doping on the magnetic properties of manganese clusters, we performed non collinear magnetic calculations within the local spin density approximation (LSDA) for the exchange-correlation. We find that the electronic properties can be better controlled when the cluster is doped with a sulphur atom, and less size dependent. There are no differences in the magnetic properties of doped and non-doped clusters, except for n=7 and 8, in which the total magnetic moment per atom are smaller in doped clusters.