Polarizabilities and hyperfine structure constants of the low-lying levels of barium

The results of ab initio calculation of energies, hyperfine structure constants and static polarizabilities for several low-lying levels of barium are reported. The effective Hamiltonian for the valence electrons has been constructed in the frame of CI+MBPT method and solutions of many electron equation were found. Using the wave functions obtained the hyperfine structure constants and static polarizabilities were calculated. Received: 22 June 1998 / Revised: 2 September 1998 / Accepted: 15 September 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     

Ascending air bubbles in protein solutions

We report measurements of the ascending velocity of air bubbles in protein (bovine serum albumin) solutions. We show that, because of the protein molecules adsorbed on their surface, the terminal ascending velocity of bubbles is strongly reduced compared to the terminal velocity in pure water: protein- covered bubbles behave hydrodynamically as solid spheres. From the evolution of the ascending velocity with time, we can derive the amount of protein needed to immobilize the bubble interface which is 0.5 mg m^-2, i.e. only one fifth of the amount adsorbed at equilibrium in the range of used bulk concentrations. Received: 6 March 1998 / Revised and accepted: 6 May 1998     

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     

Low frequency dielectric permittivity of quasi-one-dimensional conductor (TMTTF)2Br

Conductivity and permittivity of the organic transfer salt (TMTTF)₂Br have been measured at low frequencies (10²-10⁷ Hz) between room temperature down to 4 K. The real part of the permittivity, , is shown to grow below the temperature at which the conductivity is maximum due to charge localization of Mott-Hubbard type. reaches a maximum of 10⁵-10⁶ at 35 K-50 K depending on the samples. Decreasing temperature below , sharply decreases down to helium temperature through the antiferromagnetic phase transition at T _N = 15 K. We explain the magnitude, the temperature and frequency dependence of as resulting from short range charge density wave states in the temperature range where charge localization occurs. This interpretation is supported by recent X-ray scattering measurements. Received: 10 October 1997 / Revised: 28 February 1998 / Accepted: 3 March 1998     

A new approach to analyse H⊗(2h⊕g) Jahn-Teller system for C60

It is now well-known that electron (hole)-vibron coupling and hence Jahn-Teller (JT) effect is important understanding the properties of C₆₀ and related molecules. In this paper, we study H(2) coupling case to find the potential energy surfaces for the positively charged C₆₀ molecule due to distortion. The H(2) Jahn-Teller system is of particular importance as this will be the JT effect displayed by C₆₀ molecules removed with an electron. C₆₀ ⁺ is obtained by removing one electron from fivefold degenerate H_u highest occupied molecular orbital (HOMO) and a hole in HOMO interacts with the vibrational modes of C₆₀ and symmetry is broken. We apply the method of symmetry breaking mechanism to obtain expressions for the potential energy surface. Received 27 December 1999 and Received in final form 15 May 2000     

Ab initio molecular dynamics study on Ag (n = 4, 5, 6)

Ab initio Molecular Dynamics (MD) method, based on density functional theory (DFT) with planewaves and pseudopotentials, was used to study the stability and internal motion in silver cluster Ag_n, with n =4-6. Calculations on the neutral, cationic and anionic silver dimer Ag₂ show that the bond distance and vibrational frequency calculated by DFT are of good quality. Simulations of Ag₄, Ag₅, and Ag₆ in canonical ensemble reveal distinct characteristics and isomerization paths for each cluster. At a temperature of 800 K, an Ag₄ has no definite structure due to internal motion, while for Ag₅ and Ag₆the clusters maintain the planar structure, with atomic rearrangement observed for Ag₅ but not for Ag₆. At a temperature of 200 K, Ag₄ can exist in two planar structures whilst Ag₅ is found to be stable only in the planar form. In contrast Ag₆ is stable in both planar trigonal and 3D pentagonal structures. Micro-canonical MD simulation was performed for all three clusters to obtain the vibrational density of states (DOS). Received 5 May 1999 and Received in final form 20 August 1999     

Influence of hydrodynamics on the dynamics of a homopolymer

We present an analytical approach of the dynamics of a polymer when it is quenched from a solvent into a good or bad solvent. The dynamics is studied by means of a Langevin equation, first in the absence of hydrodynamic effect, then taking into account the hydrodynamic interactions with the solvent. The variation of the radius of gyration is studied as a function of time. In both cases, for the first stage of collapse or swelling, the evolution is described by a power law with a characteristic time proportional to N ^4/3 (N), where N is the number of monomers, without (with) hydrodynamic interactions. At larger times, scaling laws are derived for the diffusive relaxation time. Received: 10 March 1998 / Received in final form: 15 September 1998 / Accepted: 25 September 1998     

Charge states of transition metal in “Cr, Co and Ni” doped Ln0.5Ca0.5MnO3 CMR manganites

The XAS study at Cr, Co, Ni and Mn K-edges was performed for the doped CMR manganites Ln_0.5Ca_0.5Mn_1-xB_xO₃ with Ln=La, Nd, Sm and B= Cr, Co, Ni (), on the samples that were studied previously for their ferromagnetic-metallic to antiferromagnetic-insulator transition. We observed that the formal charges of the doping elements are Ni²⁺, Co²⁺ and Cr³⁺. It is also evidenced that the average formal charge of the manganese is increased after doping, in agreement with the charge compensation keeping “O₃” stoichiometry. These results suggest that the doping elements participate directly to the band structure. Received: 9 January 1998 / Received in final form: 6 April 1998 / Accepted: 7 April 1998     

On the stoichiometry of the organic metal bis(ethylenedioxy)-tetrathiafulvalene chloride

We report on Shubnikov-de Haas and de Haas-van Alphen measurements of an organic metal based on the molecular donor bis(ethylenedioxy)-tetrathiavulvalene (= BEDO-TTF) and the anion Cl^- with H₂O molecules. The observed single oscillation frequency perfectly follows the two-dimensional dependence with T. The Fermi-surface area of of the first Brillouin zone proves a quarter-filled band, i.e., a 2:1 stoichiometry of the BEDO-TTF donor with respect to the anion. The apparent discrepancy to X-ray data which give a 1:1 ratio between BEDO-TTF and Cl^- is understood by replacement of H₂O molecules with (H₃O)⁺ ions. The proposed stoichiometry therefore is (BEDO-TTF)₂ ⁺(H₅O₂)⁺(Cl^-)₂. The cyclotron effective mass is when deduced from the temperature dependence of the fundamental oscillation amplitude, but strongly reduced when extracted from higher harmonics. This and the strong harmonic content of the oscillations signals an influence of the two-dimensional electronic structure and can be qualitatively understood by applying the concept of magnetic interaction to the effect of the oscillatory chemical potential. Received: 16 April 1998 / Revised: 7 July 1998 / Accepted: 9 July 1998     

On the implicit integral character of Roothaan's expansion

The molecular generator coordinate Hartree-Fock method is reviewed. The connection between a quadrature solution of the generator coordinate Hartree-Fock equations and Roothaan's equations is stressed. The relation between linear expansion coefficients and generator coordinate weight functions is discussed and a numerical and analytical example is provided for the 1s orbital of the hydrogen atom represented as the integral transform of a Gaussian function. For the same example, the Gauss-Labatto quadrature is employed to emphasize the implicit integral character of Roothaan's equations. As a major conclusion, the interpretation that every LCAO calculation is actually performing integrations of the Griffin-Wheeler equations is advanced. Basis sets are therefore abscissas of the implicit quadrature used in the integration, whereas the linear coefficients automatically incorporate the corresponding weights. Subsequently, it is shown how to extract the generator coordinate weight function from the LCAO coefficients which has the advantage of being a characteristic of the physical system under study and not of the particular calculation being carried out. As such, basis set design becomes how to efficiently sample the weight function. Received: 13 June 1998 / Received in final form: 12 August 1998 / Accepted: 14 September 1998     

Vitamin E models

The molecular conformations of shortened molecular models of vitamin E (tocopherol and tocotrienol) and their sulfur and selenium congeners were studied computationally at the DFT level of theory [B3LYP/6-31G(d)]. The sequence of stabilization by the various heteroatoms was found to be the following: O∼Se > S. On the basis of the present structural results it seems that the seleno-congener of vitamin E is a distinct possibility. Received 9 May 2002 / Received in final form 9 July 2002 Published online 13 September 2002     

Relativistic and many-body effects in K, L, and M shell ionization energy for elements with and the determination of the 1s Lamb shift for heavy elements

We report on a calculation of K, L and M inner-shell ionization energy in atoms with atomic numbers in the range . Many-body effects are evaluated for all n =1, 2, and 3 hole states. Those include correlation and effects due to the auto-ionizing nature of the hole states (Auger shift). For high Z we add recent corrected nuclear polarization, and several second-order vacuum polarization corrections. K and L ionization energies are compared with experimental X-ray absorption edges measurements. Excellent agreement with rare gazes and metal vapor measurements is found. We also compare our calculations with X-ray transition energies for all K and L lines that involve K, L and M holes. Finally we use K X-ray lines to deduce an hydrogenlike 1 s Lamb shift for several heavy elements, with far better accuracy than has been obtained by direct measurements of hydrogenlike ions. Received: 25 February 1998 / Accepted: 31 March 1998     

Classical dynamical simulation of spontaneous alloying

“Spontaneous alloying” observed by Yasuda, Mori et al. for metallic small clusters is simulated using classical Hamiltonian dynamics. Very rapid alloying occurs homogeneously and cooperatively starting from the solid phase of the cluster if the heat of solution is negative and the size of cluster is less than a critical size. Analysis of 2D models reveals that the alloying rate obeys an Arrhenius-type law, which predicts the alloying time much less than second at room temperature. Evidences manifesting that the spontaneous alloying proceeds in the solid phase without melting are also presented. The simulation reproduces the essential features of the experiments. Received: 2 March 1998 / Revised: 21 May 1998 / Accepted: 28 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     

Photon statistics of a bad-cavity laser near threshold

A simple model of a bad-cavity laser is presented based on Haken's master equation for N pumped two-level atoms in a cavity. Via adiabatic elimination of fast variables the whole photon statistics is solved analytically near threshold. It is shown that the second order coherence function g ⁽²⁾ (0) has a very different behavior near threshold for a bad-cavity laser compared to a good-cavity laser. The power spectrum illustrates nicely the different time scales involved in the dynamics. Received: 13 November 1998 / Revised: 19 May 1998 / Accepted: 6 July 1998     

Plateau transitions in fractional quantum Hall liquids

Effects of backward scattering between fractional quantum Hall (FQH) edge modes are studied. Based on the edge-state picture for hierarchical FQH liquids, we discuss the possibility of the transitions between different plateaux of the tunneling conductance G. We find a selection rule for the sequence which begins with a conductance (m: integer, p: even integer) in units of e ²/h. The shot-noise spectrum as well as the scaling behavior of the tunneling current is calculated explicitly. Received 5 October 1999 and Received in final form 19 November 1999     

Electron-pair densities of group 2 atoms in their and terms

Electron-pair intracule (relative motion) and extracule (center-of-mass motion) densities are studied in both position and momentum spaces for the ¹ P and ³ P terms of the group 2 atoms Be (atomic number Z =4), Mg (Z =12), Ca (Z =20), Sr (Z =38), Ba (Z =56), and Ra (Z =88). In position space, the ¹ P - ³ P difference in the intracule densities shows that the probability of a small interelectronic distance is larger in the triplet for all the six atoms, as reported for the lightest Be atom in the literature. The position-space extracule density clarifies that the triplet electrons are more likely to be at opposite positions with respect to the nucleus than the singlet electrons for all the atoms. In momentum space, the singlet generally has a larger probability of a small relative momentum between two electrons as a na?ve manifestation of the Fermi hole in the triplet. The extracule density in momentum space shows that the ¹ P term has a distribution larger in a large center-of-mass momentum region than the ³ P term. Received: 26 August 1998 / Received in final form: 1 February 1999