Improved endohedral fullerenelike structures of silicon clusters Si31–Si39 by density functional calculations

We extensively search for the endohedral silicon-fullerene structures of Si₃₁–Si₃₉ using the combination of a tight-binding potential with the density functional theory. The resulting structures of our best candidates characterize more compact features comparing to previous isomers [J. Am. Chem. Soc. 126, 13845 (2004); J. Chem. Phys. 124, 164311 (2006)]. Most of our best candidates belong to new families featuring different core/cage combinations or different original carbon fullerene cages with respect to those of previous isomers. Energy calculations reveal that our best candidates are more stable than the previous best ones at the PW91 level, except for n = 34 and 38. The predicted relative stabilities of these isomers remain even at finite temperatures. In addition, the densities of dangling-bond atoms in the surfaces of our Si₃₃ and Si₃₉ isomers are significantly lower than the previous best candidates, as well as lower than those of their neighbors. This finding together with the densities of the active sites in the surfaces of the previous best candidates of Si₃₄ and Si₃₈ is roughly consistent with the observed relative reactivities of the silicon clusters in the size range of n = 31-39.     

Manipulation of nanoparticles using dynamic force microscopy: simulation and experiments

82 , M = Sc, Y, La) are discussed. The first ¹³C hyperfine structure has been analyzed in detail and at least seven electronically different groups of carbon atoms could be assigned by simulations of the ESR spectra. The strong similarity of the ¹³C satellite structure suggests the preference of one cage isomer for the scandium group C₈₂ endohedrals. The geometric structure and the electronic structure of all nine fullerene cage isomers of La@C₈₂ were studied by approximate density-functional-based theoretical calculations. A C_3v isomer was found as the most stable one. The manifold of ¹³C hyperfine coupling constants could be interpreted on the basis of the calculated spin density distributions. Received: 15 September 1997/Accepted: 16 October 1997     

Infrared absorption-edges of molecular nonlinear optical crystals: an <Emphasis Type="Italic">ab initio</Emphasis> calculation

A theoretical model suitable for calculating infrared absorption-edges of molecular nonlinear optical (NLO) crystals is introduced from high-level calculations of molecular vibrational spectra. The model is useful for elucidating the relationship between the molecular vibration and macroscopic absorption edges on the IR side of organic nonlinear optical crystals. The first-principle ab initio method carries out the calculations of IR absorption-edges of several typical molecular NLO crystals. These molecular NLO crystals include urea, 2-methyl-4-nitroaniline (MNA), meta-dinotrobenzene (MDNB), 3-methyl-4-methooxy-4^′-nitrostilbene (MMONS), and 3-hydroxyl-4^′-nitrostilbene (HMONS). The calculated results are compared with the measurements and good agreement is found between them. The experimentally unknown values of IR absorption-edges of some new synthesized crystals are predicted. The theoretical analyses of the structural origins of IR absorption cut-offs are discussed. The results are helpful for the molecular simulation and design of potential infrared molecular NLO crystals. Received: 9 April 2002 / Accepted: 18 July 2002 / Published online: 28 October 2002 RID="*" ID="*"Corresponding author. Fax: +86-591/3714946, E-mail: wkc@ms.fjirsm.ac.cn     

Rare-gas-induced broadening and shift of two-photon transitions to intermediate Rydberg states of atomic thallium*

Results of broadening and shift measurements of Doppler-free two-photon lines for transitions from the ground state to the Rydberg states with intermediate principle quantum numbers of atomic thallium perturbed by rare gases are reported. The rates show a distinct behaviour in this range of principle quantum numbers and significant dependence on the total angular momentum of the upper nP state. The experimental results are compared with calculations using a Van der Waals potential and a superposition of polarization and Fermi potentials. Additionally, broadening and shift rates of the transition Tl 6P _3/2 -9P _3/2 have been measured for quadrupolar as well as for mainly scalar excitation. The rates for both kinds of excitation coincide within the limits of error reflecting the small perturbation of the 6P _3/2 state compared to that of the upper 9P _3/2 state. Received: 6 August 1997 / Revised in final form: 29 November 1997 / Accepted: 11 December 1997     

Electron density and Fisher information of Dirac-Fock atoms

Numerical calculations on the gradient and Laplacian forms of the position space Fisher information measure are reported using the 1-normalised Dirac-Fock densities (shape function), σ(r), for atoms H-Lr. It is shown that the difference in effective electrostatic potentials, corresponding to the gradient and the Laplacian form of Fishers' information, is completely defined by the shape function (the density per particle) at the nucleus, σ(r=0). The influence of relativistic effects on the Fisher information is recovered for the first time.     

Characterization of the Fermi surface of the organic superconductor - by measurements of Shubnikov-de Haas and angle-dependent magnetoresistance oscillations and by electronic band-structure calculations

The electronic structure of the quasi two-dimensional (2D) organic superconductor -(ET)₂SF₅CH₂CF₂SO₃ was examined by measuring Shubnikov-de Haas (SdH) and angle-dependent magnetoresistance (AMRO) oscillations and by comparing with electronic band-structure calculations. The SdH oscillation frequencies follow the angular dependence expected for a 2D Fermi surface (FS), and the observed fundamental frequency shows that the 2D FS is 5% of the first Brillouin zone in size. The AMRO data indicate that the shape of the 2D FS is significantly non-circular. The calculated electronic structure has a 2D FS in general agreement with experiment. From the temperature and angular dependence of the SdH amplitude, the cyclotron and band effective masses were estimated to be and ,where g is the conduction electron g factor and the free electron mass. The band effective mass is estimated to be from the calculated electronic band structure. Received: 3 March 1997 / Revised: 5 May 1997 / Received in final form: 5 November 1997 / Accepted: 10 November 1997     

Can we rationalize the structure of small silicon-carbon clusters?

A theoretical study of clusters with using density functional theory is presented. Tests of various functionals demonstrate that local spin density approximation (LSDA) is the most adequate functional for the study of these systems. Structures, vibrational frequencies, and IR intensities of the lowest energy isomer of the studied clusters obtained using LSDA are described, and the unusual properties of the Si-C clusters are discussed. A quantitative analysis of the obtained structures was carried out, and relations between the coordinations, interatomic distances, and angles observed in the Si-C clusters were obtained through introduction of the notion of coordination. This analysis also shows that the carbon atoms mainly exhibit sp and sp² hybridizations, and that a majority of silicon atoms do not hybridize. This study is the fi rst step of the implementation of a semi-empirical potential, which would describe the moderately small Si-C clusters. Received: 20 October 1997 / Received in final form: 16 December 1997 / Accepted: 17 December 1997     

Collectivity in the optical response. of small metal clusters

The question of whether the linear absorption spectra of metal clusters can be interpreted as density oscillations (collective “plasmons”) or can only be understood as transitions between distinct molecular states is still a matter of debate for clusters with only a few electrons. We calculate the photo-absorption spectra of Na₂ and Na₅ ⁺ comparing two different methods: quantum fluid dynamics and time-dependent density functional theory. The changes in the electronic structure associated with particular excitations are visualized in “snapshots” via transition densities. Our analysis shows that even for the smallest clusters, the observed excitations can be interpreted as intuitively understandable density oscillations. For Na₅ ⁺, the importance of self-interaction corrections to the adiabatic local density approximation is demonstrated. Received: 1 July 2001 / Published online: 10 October 2001     

Electroluminescent properties of dimeric bis(2-(2′-hydroxyl phenyl)benzthiazolate)zinc (II) complex

A blue shifted photoluminescent emission in bis(2-(2′-hydroxyl phenyl)benzthiazolate)zinc (II) complex, ZBZT, arises out of the dimeric structure, typical of the localized electron density around the non-bridged ligand in the excited state of the complex. An average decay lifetime of 4.8 and 3.0 ns for the ligand and the complex, respectively indicates an energy transfer from the ligand to the metal. A PL quantum efficiency of about ?_ZBZT=0.45 in DMF solution is observed, in comparison to the Alq₃, complex, ?_Alq3=0.116. Semi empirical ZINDO/S-SCF-CI calculations support the dominance of non-bridged ligand moiety in controlling the photoluminescent properties. An unusually broad white light (FWHM ∼220 nm) electroluminescent emission in the two layer device structure brings out the features of an exciplex formation between the active layer ZBZT/TPD interface, which is studied at different current densities. Such a broadened emission is verified for different thicknesses of the active layer substantiating the role of exciplex formation.     

Spherical averaged jellium model with norm-conserving pseudopotentials

The effect of non-local norm-conserving pseudo-potentials on the static and dynamic properties of Na_n and Li_n cluster with n=6,8 is investigated in the frame of self-consistent LDA calculations with spherically averaged ionic density (SAPS model). A comparison with previous calculations which use local pseudo-potentials as well with uniform averaged non-local pseudo-jellium calculation has been carried out. A better quantitative agreement with experiments has been found in the calculation of the photoresponse cross-section with respect to either simple jellium or pseudo-jellium model, even in very small clusters, where deviations from sphericity are not negligible. Received: 3 March 1998 / Received in final form and Accepted: 2 June 1998     

Quantitative comparison of different preionization schemes of KrF laser discharges

* fluorescence radiation from the ion–ion recombination process in the gas volume during the preionization phase, therefore allowing spatial resolution by partial imaging of the volume. Volume-integrated and temporally resolved measurements are carried out to determine the average of absolute preionization densities by comparison with a theoretical model of the temporal behaviour of the recombination process. Spatially resolved measurements reveal the distribution of the preionization density. The preionization densities determined from spark and sliding/corona discharges schemes are considerably higher (n_e ⁰?10¹² cm^-3) than those obtained from pulsed X-ray preionization (n_e ⁰?10⁷ cm^-3). Received: 3 October 1997/Revised version: 6 January 1998     

Energy pooling in caesium vapour:

The total rate coefficient k for the energy pooling process has been measured in dependence on the ratio of the number densities of the Cs 6P fine-structure sublevels. The measurements were performed applying the laser fluorescence method. From the set of the obtained data for k, the rate coefficients for the particular collisions were derived. The obtained values for the and collisions at T = 600 K are , and , respectively. The value for k₁ and the estimate for k₃ are consistent with the data previously published by other authors. The rate coefficient k₂ is reported for the first time. Received: 10 June 1997 / Revised: 13 October 1997 / Accepted: 5 January 1998     

Predictions of geometrical structures and ionization potentials for small barium clusters Ba

The geometrical structure of ground state Ba_n clusters (n =2-14) has been predicted from various types of calculations including two ab initio approaches used for the smaller sizes namely HF+MP2( n =2-6), DFT (LSDA)( n =2-6, 9) and one model approach HF+pairwise dispersion used for all sizes investigated here. The lowest energy configurations as well as some isomers have been investigated. The sizes n =4, 7 and 13 are predicted to be the relatively more stable ones and they correspond to the three compact structures: the tetrahedron, the pentagonal bipyramid and the icosahedron. The growth behavior from Ba₇ to Ba₁₃ appears to be characterized by the addition of atoms around a pentagonal bipyramid leading to the icosahedral structure of Ba₁₃ which is consistent with the observed size-distribution of barium clusters. Values for vertical ionization potentials calculated for n =2-5 at the CI level are seen to be in quite good agreement with recent measures. Received: 14 May 1997 / Received in final form: 2 February 1998 / Accepted: 27 February 1998     

Stark broadening of the hydrogen Paschen <Emphasis Type="Bold">γ</Emphasis> transition at electron densities of the order of cm

Stark broadening measurements and calculations of the Paschen γ spectral line of hydrogen ( λ = 1.094[: MU :] m) are reported. Investigations have been performed at plasma electron densities between 1.4×10 ¹⁵ cm ^-3 and 3.7×10 ¹⁵ cm ^-3 . As the light source a wall-stabilized arc operated in a helium-hydrogen gas mixture at atmospheric pressure has been applied. The radiation of the plasma emitted from nearly homogeneous plasma layers in end-on direction, was measured with the use of a grating spectrometer equipped with a charge coupled device (CCD) detector. The radiance calibration was carried out against light outputs originating from a tungsten strip radiation standard. The measured FWHM are compared with results of our calculations based on computer simulation techniques (full computer simulation method -- FCSM). Our broadening data are also compared with results of other theoretical approaches (MM-method, quasi-static approximation) and with experimental data obtained at electron densities about one order of magnitude larger than ours. Received 21 January 2003 Published online 24 April 2003 RID="a" ID="a"e-mail: wujec@uni.opole.pl     

Density functional theory investigation of S2 in KCl: evidence for the existence of a di-vacancy site

Electron paramagnetic resonance experiments have shown that, depending on the doping procedure, two different S₂⁻ centers may coexist in KCl. These centers have the ²B_2g and the ²B_3g ground state, respectively. As no experimental ligand hyperfine data are available, it could not be determined whether the S₂⁻ molecular ion replaces a single halide ion (mono-vacancy site) or two nearest neighbor halide ions (di-vacancy site). Also, other defect models could a priory be considered. In this work, cluster in vacuo density functional theory calculations of the g and ³³S hyperfine tensors show that the S₂⁻ ion at a mono-vacancy site has the ²B_2g ground state, whereas S₂⁻ in a di-vacancy exhibits a ²B_3g ground state. For the latter center, the possibility of charge compensation by a cation vacancy is also considered. The calculations indicate that a possible vacancy is not in the direct vicinity (nearest or next-nearest neighbor) of the S₂⁻ ion.     

Magnetic phase diagram of perovskite Mn oxides at T = 0

Minimizing total free energy by numerical calculations, we obtain the magnetic phase diagram of perovskite Mn oxides, such as with , Ca, Sr, etc. in the whole doping region from x =0 to x =1 at temperature T =0. It is discovered that a spiral state is stable in a low concentration of X ions while a canted state is stable in a high concentration of X ions, and a ferromagnetic phase can exist in the intermediate concentrations when the antiferromagnetic interaction is weak. The energy difference between spiral and canted states is found to be small when the Hund coupling is large. Magnetic field induced spiral/canted phase transition is considered as a possible mechanism of the colossal magnetoresistance (CMR) in the Mn oxides. Received: 11 July 1996 / Revised: 7 December 1996 / Accepted: 24 July 1997     

Assessment of adiabatic local-density approximation for nonlinear optical properties

Employing a near exact Hylleraas wavefunction we calculate various third-order nonlinear optical properties for the helium atom within the time-dependent Kohn-Sham theory. In our calculations we employ the adiabatic local-density approximation (ALDA) for the exchange and correlation kernels f_xc and g_xc, and compare the numbers obtained by us with the available accurate theoretical as well as experimental results. Our results demonstrate the accuracy of ALDA for the calculation of nonlinear optical properties of many electron systems. Received: 22 June 1998 / Accepted: 15 October 1998     

Influences of thermal annealing, the electrolyte pH, and current density on the interface state density distribution of anodic MOS structures

2 /p-Si MOS structures were prepared in 0.1 M K₂SO₄ electrolyte with a pH of 7 (the 0.1 M KOH solution was buffered with H₂SO₄) at current densities of 3, 5, and 7 mA/cm² and with four different pH values of the electrolyte at 3 mA/cm². It is found that thermal annealing at a relatively low temperature can be used to improve the anodic MOS characteristics. Moreover, of the pH and current density it followed that the pH has a dominant role in the interface electrical properties. The lowest interface state densities at the maximum and the midgap positions are 7.1×10¹¹ and 2.7×10¹⁰ eV^-1cm^-2 for a sample made with pH=7, J=3 mA/cm². The characteristics of this sample seem satisfactory for device applications of anodized p-Si. Received: 8 July 1996/Accepted: 22 January 1997     

Visualisation of a supersonic free-jet expansion using laser-induced fluorescence spectroscopy: Application to the measurement of rate constants at ultralow temperatures

2 Σ⁺, v^′=0) by air at 26±4 K. A value of 2.56±0.40×10^-10 molecule^-1 cm³ s^-1 was obtained, a factor of more than four higher than at room temperature, and consistent with attractive forces dominating the quenching of OH(A²Σ⁺). A d etailed computational fluid dynamics (CFD) simulation of the supersonic free-jet expansion was performed, providing a two-dimensional visualisation of temperature and density variations throughout the expansion. The CFD calculations reproduced the salient features of the experimental temperature and density profiles along the centreline. Comparison between experiment and computation has allowed validation of CFD codes. Received: 31 January 1997/Revised version: 24 March 1997     

Electronic structure and driving forces in α-cyclodextrin:butylparaben inclusion complexes

We investigate the geometry and electronic structure for complexes of α-cyclodextrin with butylparaben using DFT and Hartree-Fock calculations. The effect of solvent is explicitly taken into account. A Morokuma-Kiatura analysis of the bond energy is performed. We emphasize the role of the water, by pointing out the changes in the solvent's electronic structure for different docking geometries.