Theoretical and computer simulation study of density fluctuations in liquid binary alloys

The dynamical properties of liquid alloys are investigated by means of memory function equations and molecular-dynamics simulation. A simple model for the second-order memory function in a binary liquid, based on Mori's memory function formalism, is proposed and applied in numerical calculations of the time correlation functions and dynamic structure factor of liquid K_0.7Cs_0.3 and K_0.3Cs_0.7 alloys. Obtained results are discussed in comparison with the results of computer simulations. Received: 27 February 1998 / Revised: 24 July 1998 / Accepted: 27 July 1998     

Fragmentation of water clusters: Molecular-dynamics simulation study

The fragmentation of water clusters, [(H ₂ O)_n;n = 2-8], have been investigated by using molecular-dynamics simulation method. In the simulations a polarizable-dissociable potential energy function for water has been used. Particular attention has bee paid to investigate the effect of structural properties and cluster size on the fragmentation. Received 27 April 2000 and Received in final form 6 October 2000     

Simulation of Raman spectra of C and C by non-orthogonal tight-binding molecular dynamics

A non-orthogonal tight-binding molecular-dynamics formalism is used to simulate Raman spectra of the fullerene molecules C₆₀ and C₇₀. Two parametrization schemes for the Hamiltonian and the overlap matrix elements are investigated. The considered molecules are excited randomly and the Fourier transform of the displacement autocorrelation function is employed to extract the vibrational properties. Fair agreement with experiment and with force-constant and ab initio calculations is achieved, with comparatively smaller maximum errors in the frequencies than for other molecular dynamics or semi-empirical calculations from the literature. Received 4 February 1999 and Received in final form 28 November 1999     

Ab initio thermodynamic properties for different isomers of the AlO molecule

We present ab initio thermodynamic properties for seven different geometric isomers of molecular Al₂O₃ over a wide temperature range. The rigid rotator-harmonic oscillator approximation is used to calculate the partition function as it is generally applied in thermodynamic studies of polyatomic molecules. The molecular data employed in setting up the partition functions are taken from the theoretical results of ab initio MP2/6-31G(d) calculations. An analysis of the effects of the various contributions is made. The resulting thermodynamic functions of Al₂O₃ are consistent with the JANAF thermochemical data compilation. Some thermochemical implications are discussed. Received: 9 September 1998 / Received in final form: 2 October 1998     

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     

Structural and vibrational properties of C36 and its oligomers (C36) M = 2, 3, 4 by tight-binding molecular dynamics

Non-orthogonal tight-binding molecular-dynamics is employed to calculate structural and vibrational properties of C₃₆ and its oligomers (C₃₆) _{M = 2, 3, 4} . The lowest energy configuration of the C ₃₆ cage is confirmed to have D _6h symmetry. For the dimer, too, the D _2h structure reported in the literature is found. The vibrational spectrum is identified with the power spectrum of the displacement autocorrelation function. Additional vibrational properties are extracted from the dynamical matrix. For the monomer, fair agreement with available ab initio calculations is achieved, with comparatively smaller deviations in the Raman-frequencies than for published semi-empirical calculations. The features of the vibrational modes are correlated with the structural properties of the oligomers. Received 24 November 2000 and Received in final form 24 August 2001     

Coexistence of antiferromagnetic and ferromagnetic phase for ferromagnetic Kondo lattice model

To study the proposed phase separations in doped manganites, we performed Monte-Carlo calculations for the ferromagnetic Kondo lattice model with strong Hund's coupling between conduction electrons and localized spins. For the practical calculations, we adopted a one dimensional lattice and treated the spins of the localized t_2g electrons semi-classically. A direct evidence of the phase separation is observed from a snapshot of the spatial dependence of localized spins. No indication of the canted or spiral phases is found in the results of simulations. Further, the calculated results of the spin structure factor in the phase separation region are well compared with recent experiments. Received: 1st September 1998 / Revised: 30 October 1998 / Accepted: 27 November 1998     

Block persistence

We define a block persistence probability p _l (t) as the probability that the order parameter integrated on a block of linear size l has never changed sign since the initial time in a phase-ordering process at finite temperature T<T _c . We argue that in the scaling limit of large blocks, where z is the growth exponent (), is the global (magnetization) persistence exponent and f(x) decays with the local (single spin) exponent for large x. This scaling is demonstrated at zero temperature for the diffusion equation and the large-n model, and generically it can be used to determine easily from simulations of coarsening models. We also argue that and the scaling function do not depend on temperature, leading to a definition of at finite temperature, whereas the local persistence probability decays exponentially due to thermal fluctuations. These ideas are applied to the study of persistence for conserved models. We illustrate our discussions by extensive numerical results. We also comment on the relation between this method and an alternative definition of at finite temperature recently introduced by Derrida [Phys. Rev. E 55, 3705 (1997)]. Received: 25 February 1998 / Revised: 24 July 1998 / Accepted: 27 July 1998     

An universal relation between fractal and Euclidean (topological) dimensions of random systems

It is shown that a dimension-invariant form for fractal dimension D of random systems (where d is Euclidean dimension of the embedding space) is in good agreement with results of numerical simulations performed by different authors for critical (p=p _c ) and subcritical (p<p _c ) percolation, for lattice animals, and for different aggregation processes. Received: 9 July 1998 / Revised and Accepted: 12 July 1998     

Excess thermodynamic properties of liquid mixtures of methane and perfluoromethane

New intermolecular potentials, derived in part from ab initio calculations, have been used in molecular-dynamics simulations of liquid mixtures of CH₄ and CF₄. Results for the excess volumes and excess enthalpies are found to be in excellent agreement with experimental data. Structural features of the simulated mixtures are strongly suggestive of a tendency to demix.     

Surface coverage studies of the icosahedron by Li using density based molecular dynamics

Density based molecular dynamics has been used to investigate the ground state structures of heterogeneous binary clusters Al₁₃Li_n, n = 1, 2, 3, 4, 10, 19, 20, 21. Some of these structures have also been investigated by full Kohn-Sham based calculations. Our earlier investigations have shown that in the Al-Li cluster, the ground state configurations are the ones where the Al atoms form a core around which the Li atoms form a “cage”. In the present work, we have chosen the well-known Al₁₃ icosahedron as the surface over which we study the evolution of the surface coverage as the number of Li atoms increases. On the basis of the earlier work, we expect that the Al₁₃Li₂₀ cluster would be the most stable and indeed our simulations do yield such a novel fivefold symmetric stable structure formed out of purely metal atoms. This icosahedral substrate is also used to study the coverage of the aluminum surface by lithium atoms. For a small number of Li atoms, these studies suggest that the Li-Li dimerisation is not particularly favored. Received: 24 October 1997 / Revised: 7 April 1998 / Accepted: 29 June 1998     

Dynamics of polymeric manifolds in melts: the Hartree approximation

The Martin-Siggia-Rose functional technique and the selfconsistent Hartree approximation is applied to the dynamics of a D-dimensional manifold in a melt of similar manifolds. The generalized Rouse equation is derived and its static and dynamic properties are studied. The static upper critical dimension, d _uc =2D/(2-D), discriminates between Gaussian (or screened) and non-Gaussian regimes, whereas its dynamical counterpart, , discriminates between Rouse- and renormalized-Rouse behavior. The Rouse modes correlation function in a stretched exponential form and the dynamical exponents are calculated explicitly. The special case of linear chains D=1 shows agreement with Monte-Carlo simulations. Received: 22 May 1998 / Received in final form: 31 August 1998 / Accepted: 8 September 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     

Numerical study of local and global persistence in directed percolation

The local persistence probability P _l (t) that a site never becomes active up to time t, and the global persistence probability P _g (t) that the deviation of the global density from its mean value does not change its sign up to time t are studied in a (1+1)-dimensional directed percolation process by Monte-Carlo simulations. At criticality, starting from random initial conditions, P _l (t) decays algebraically with the exponent . The value is found to be independent of the initial density and the microscopic details of the dynamics, suggesting is an universal exponent. The global persistence exponent is found to be equal or larger than . This contrasts with previously known cases where . It is shown that in the special case of directed-bond percolation, P _l (t) can be related to a certain return probability of a directed percolation process with an active source (wet wall). Received: 15 December 1997 / Revised: 6 April 1998 / Accepted: 29 May 1998     

How to get access to long range states of highly excited molecules

Due to competition between ionic and covalent dissociation, the excited potential curves of the alkali dimers display long range structures, leading in some cases to secondary wells. We discuss the possibility of populating the well (with a depth of 1614.8 cm^-1, located at R _e = 30.5a ₀ ) that is present in the Na₂ potential curve and propose detection schemes. Received: 28 May 1998 / Revised: 5 August 1998 / Accepted: 24 September 1998     

Isotope effects on the electronic critical points of germanium: Ellipsometric investigation of the and transitions

Within the past years the optical excitations of electrons have been measured for semiconductor samples of different isotope compositions. The isotope shift observed have been compared with calculations of the effects of electron-phonon interaction on the electronic band structure. While qualitative agreement has been obtained, some discrepancies remain especially concerning the E₁ and transitions. We have remeasured the effect of isotope mass on the E₁ and transitions of germanium with several isotopic compositions. The results, obtained by means of spectroscopic ellipsometry, confirm that the real part of the gap self-energies induced by electron-phonon interaction is larger than found from band structure calculations, while the imaginary part agrees with those calculations, which are based on a pseudopotential band structure and a bond charge model for the lattice dynamics. Our results agree with predictions based on the measured temperature dependence of the gaps. We compare our data for E₁ and with results for the lowest direct (E₀) and indirect (E_g) gaps. The measured values of and increase noticeably with increasing isotope mass. Similar effects have been observed in the temperature dependence of in and . A microscopic explanation for this effect is not available. Received: 6 March 1998 / Revised: 27 April 1998 / Accepted: 15 May 1998     

Photoionization thresholds and structures of third group metals clustered with ammonia

A photoionization study of the Me(NH₃) clusters formed in the reaction of photoablated third group metal vapor with gaseous ammonia is reported. The photoionization spectra exhibit some features due to vibrational excitation of ionic clusters and to transitions to neutral Rydberg states leading to autoionization. DFT quantum chemical calculations are performed on the Me(NH₃). The cluster geometries are fully optimized imposing the C_3v symmetry. The calculated values of the IPs are in agreement with those experimentally determined. Received: 16 February 1998 / Revised and Accepted: 7 May 1998     

A molecular dynamics study of the structural change differences between Au225 and Au369 clusters on MgO surfaces at low temperature

The differences in structural change between Au₂₂₅ and Au₃₆₉ clusters with their (111) facets supported on MgO(100) surfaces at 5 K are studied by using molecular-dynamics simulations with the atomic interchange potentials of the Au/MgO interface. The parameters are obtained from the ab initio energies using the Chen-Möbius inversion method. Analyses of the pair distribution functions show that the two Au clusters use different deformation processes to adjust the distances between the interface atoms, owing to the misfit between the atom distances among the clusters and the substrates. The local structural changes are identified by atomic density profiles.     

Flow birefringence and stress optical law of viscoelastic solutions of cationic surfactants and sodium salicylate

The optical and rheological properties of different viscoelastic solutions of surfactant are studied in order to gather experimental data used to calculate the value of the stress optical coefficient C. Three surfactants of the same family (CTAB) have been chosen; they differ by the length of the hydrocarbon chain; it concerns the dodecyltrimethylammonium bromide (C₁₅H₃₄BrN or DoTAB), the myristyltrimethylammonium bromide (C₁₇H₃₈BrN or MyTAB), and the hexadecyltrimethylammonium bromide (C₁₉H₄₂BrN or CTAB). Different parameters like the temperature of the solution and the salinity of the solvent have been made to vary. Flow birefringence experiments and rheological measurements are performed on these solutions in order to study the dependence of the extinction angle , of the birefringence intensity and of the shear stress with the shear rate . These data are used to check the stress optical law which turns out to be valid in a wide range of shear rates. The stress optical coefficient C is then computed: it is found to vary with the salinity of the solvent and the temperature of the solution for a given surfactant. Then, for all solutions of this work the variations of C are related to the variations of the polarizability anisotropy and the persistence length. Received: 18 February 1998 / Revised: 23 June 1998 / Accepted: 22 July 1998     

Elastic scattering of low-energy electrons by NO

We report elastic integral, momentum transfer and differential cross sections for electron scattering by N₂O for energies up to 50 eV. These results were obtained at the static-exchange approximation with the Schwinger Multichannel Method with Pseudopotentials [M.H.F. Bettega, L.G. Ferreira and M.A.P. Lima, Phys. Rev. A 47, 1111 (1993)]. In general our results show good agreement with experimental data and with other theoretical results but some discrepancies are found. We have also found a shape resonance around 4 eV in agreement with previous calculations using the R-matrix Method of Sarpal et al. [J. Phys. B 29, 857 (1996)]. On the other hand, the existence of a resonance at about 13 eV, clearly seen by the Schwinger Variational Iterative Method [Michelin et al., J. Phys. B 29, 2115 (1996)], can not be confirmed by our calculations. At this energy, our cross sections show a broad bump with no clear resonant behavior given by the eigenphase sum. Received: 13 November 1997 / Revised: 13 March 1998 / Accepted: 9 April 1998