Ab initio study of the chemical states of water on Cr2O3(0 0 0 1): From the isolated molecule to saturation coverage

The reactivity of the (0 0 0 1)-Cr–Cr₂O₃ surface towards water was studied by means of periodic DFT + U. Several water coverages were studied, from 1.2H₂O/nm² to 14.1H₂O/nm², corresponding to ¼, 1, 2 and 3 water/Cr at the (0 0 0 1)-Cr₂O₃ surface, respectively. With increasing coverage, water gradually completes the coordination sphere of the surface Cr atoms from 3 (dry surface) to 4 (1.2 and 4.7H₂O/nm²), 5 (9.4H₂O/nm²) and 6 (14.1H₂O/nm²). For all studied coverages, water replaces an O atom from the missing above plane. At coverages 1.2 and 4.7H₂O/nm², the Cr–O_s (surface oxygen) acid–base character and bond directionality govern the water adsorption. The adsorption is molecular at the lowest coverage. At 4.7H₂O/nm², molecular and dissociative states are isoenergetic. The activation energy barrier between the two states being as low as 12 kJ/mol, allowing protons exchanges between the OH groups, as evidenced by ab inito molecular dynamics at room temperature. At coverages of 9.4 and 14.1H₂O/nm², 1D- (respectively, 2D-) water networks are formed. The resulting surface terminations are –Cr(OH)₂ and –Cr(OH)₃– like, respectively. The increased stability of those terminations as compared to the previous ones are due to the stabilization of the adsorbed phase through a H-bond network and to the increase in the Cr coordination number, stabilizing the Cr (t_2g) orbitals in the valence band. An atomistic thermodynamic approach allows us to specify the temperature and water pressure domains of prevalence for each surface termination. It is found that the –Cr(OH)₃-like, –Cr(OH)₂ and anhydrous surfaces may be stabilized depending on (T, P) conditions. Calculated energies of adsorption and OH frequencies are in good agreement with published experimental data and support the full hydroxylation model, where the Cr achieves a 6-fold coordination, at saturation.     

Network Forming Fluids: Yukawa Square-Well <Emphasis Type="Italic">m</Emphasis>-Point Model

Thermal and connectivity properties of the Yukawa square-well m-point (YSWmP) model of the network forming fluid are studied using solution of the multidensity Ornstein-Zernike and connectedness Ornstein-Zernike equations supplemented by the associative mean spherical approximation (AMSA). The model is represented by the multicomponent mixture of Yukawa hard spheres with m_s^am_{s}^{a} square-well sites, located on the surface of each hard sphere. To validate the accuracy of the theory, computer simulation is used to calculate the structure, thermodynamic and connectivity properties of the one-component YSW4P version of the model which is compared against corresponding theoretical data. In addition, connectivity properties of the model were studied using Flory-Stockmayer (FS) theory. Predictions of the AMSA for the thermal properties of the model (radial distribution functions (RDF), internal energy, pressure, fractions of the particles in different bonding states) are in good agreement with computer simulation predictions. Similarly, good agreement was found for the connectedness RDF (CRDF), except for the statepoints located close to the percolation threshold, where the theory fails to reproduce the long-range behavior of the CRDF. Results of both theories (AMSA and FS) for the mean cluster size are reasonably accurate only at low degrees of association. Predictions of the FS theory for the percolation lines are in a good agreement with computer simulation predictions. AMSA predictions of percolation are much less accurate, where corresponding percolation lines are located at a temperatures approximately 25% lower then those calculated using computer simulation.     

The Pauli Principle and the Restricted Primitive Model

The restricted primitive model is an electrically neutral, classical model consisting of hard spheres charged either +q or –q. We show that, by appropriately selecting the diameter of the hard spheres, the pressure when q=0 can be made equal to that for a fluid of Maxwell–Boltzmann point ions and an ideal Fermi gas of electrons. We compare the series expansion of these classical and quantum systems and find that, except for intermediate de Broglie density and moderate to strong electrical interaction strength, the restricted primitive model gives a reasonable representation of the pressure of the corresponding quantum system. Much of the current interest, however, has been focused on the above, excepted region.     

Ion beam mixing and sputtering of Kr-irradiated TiN films measured with RBS,RNRA, and PIXE

Thin titanium nitride films of 10–300 nm thickness were irradiated with ⁸⁴Kr ions of 80–700 keV energy and fluences ranging from 10¹⁶ cm² to 2×10¹⁷ cm². Sputter yields (Y=0.4–1.0) and mixing rates (k=0.05–0.5 nm⁴) were determined using the depth profiling methods RBS, RNRA, and PIXE. While the sputter yields agree well with the modified Sigmund theory, the energy dependence of the mixing rates cannot be explained by standard models.     

Neutron diffraction study of Fe83B17 metallic glass

The structure factorS(Q) was measured up to high momentum transfer,_max720 nm^–1 for Fe₈₃B₁₇ metallic glass sample. A ribbon sample was prepared by rapid quenching of the melt. In the alloy boron enriched with¹¹B isotope was used. The scattering neutron spectra were measured by the time-of-flight method at the IBR-30 facility of JINR in Dubna. The scattering angles of 30°, 60° and 150° were chosen to cover the scattering vector,Q, from 10nm^–1 up to 720nm^–1. The scattered spectra of vanadium were measured for the detector efficiency determination and those of molybdenum for the calibration. The reduced pair distribution functionG(r) was obtained using the Fourier transform ofS(Q). The atomic distances and the partial coordination numbers were calculated. It was found that the fluctuation of the Fe-B distance is larger than that of the Fe-Fe atomic pair. The chemical short-range parameter is equal to 44% of the maximum possible value.Dedicated to the memory of M. Gmitro.The sample of amorphous metallic material was kindly prepared by Dr. P. Duhaj. We would like to thank Dr. P. vec for microscoping our sample and for stimulating discussions.     

Long-wavelength behavior of the optimal HNC/O solution for the ground-state of homogeneous liquid4He atT=0 K

The long-wavelength behavior of the two-body correlation factor,u(k), of the ground-state wave function for an homogeneous liquid⁴He at zero temperature is studied. The solutions are obtained from a paired-phonon-analysis within the HNC/O approximation. The cut-off for the phonons is investigated analyzingu(k) at small momenta. It is shown that the numerical results: (a) rule out a pure gaussian cut-off and (b) are in good agreement with the exponential cut-off suggested by Chester and Reatto. The first-sound velocityc ₁ and the cut-off momentumk _c are determined at several densities in the range 0.016–0.025 Å^–3. In addition, a parametrization of these quantities as a function of the density is provided.     

Upon the utility of spherical harmonic expansions in the evaluation of cluster integrals

A novel procedure for the analytic evaluation of cluster integrals is given. By means of a result of Silverstone and Moats which transforms the spherical harmonic expansion of a function around a given point into a new spherical harmonic expansion around a displaced point, a 3N-dimensional cluster integral forN point particles (N > 2) may be reduced to 2N+1 trivial integrals andN– 1 interesting integrals, an improvement over the usual reduction to six trivial integrals and3N–6 nontrivial integrals. For hard spheres, theN–1 integrals involve only a series of simple polynomials taken between linear algebraic bounds.This work was supported in part by the National Science Foundation under Grant No. CHE79-20389.     

Ionic distribution and polymer conformation, near phase separation, in sodium polyacrylate/divalent cations mixtures: small angle X-ray and neutron scattering

Anomalous small angle X-ray scattering experiments show that before demixion in sodium polyacrylate/cobalt and sodium polyacrylate/calcium mixtures all the divalent counterions are in the close vicinity of the polyacrylate chain. The present results are consistent with previous UV/VIS spectroscopy, which have shown that all cobalt ions are chemically associated with acrylate groups. The chemical association dehydrates the acrylate monomers. However, the hydrophobicity of the complexed monomers is not strong enough to induce a collapse of the polymer chain at small spatial scale before the demixion. Indeed, the scattered intensity (X-ray and neutron scattering) decreases with the scattering vector q as q^-x with for q > 0.1 nm ^-1 which indicates that the local conformation of the chain is Gaussian. Received 21 January 1999     

Simple model for attraction between like-charged polyions

We present a simple model for the possible mechanism of appearance of attraction between like charged polyions inside a polyelectrolyte solution. The attraction is found to be short ranged, and exists only in the presence of multivalent counterions. It is produced by the correlations in layers of condensed counterions surrounding each polyion and is only weakly temperature dependent. We find the attraction to be maximum at zero temperature and dimish as the temperature is raised. The attraction is only possible if the number of condensed counterions exceeds the threshold, , where is the valence of counterions and Z is the polyion charge. Received 10 March 1999 and Received in final form 20 April 1999     

Long-wavelength behavior of the optimal HNC/0 solution for the ground state

The ground-state wave function for a two-dimensional homogeneous liquid⁴He at zero temperature is obtained from a paired-phonon analysis within the HNC/0 approximation. The long-wavelength behavior of the two-body correlation factor,u(q), is studied by following the procedure previously applied to three-dimensional bulk systems. It is shown that a cut-off law for the phonons can be determined by analyzingu(q) at small two-dimensional momentaq. The numerical results strongly support an exponential cut-off similar to that suggested by Chester and Reatto for the bulk liquid. The first-sound velocityc ₁ and the cut-off momentumq _c are calculated at several densities in the range 0.028–0.080 Å^–2.     

The stability limit of the fluid phase of polydisperse sticky spheres

It has been shown by Stell (1991, J. statist. Phys., 63, 1203) that at low temperature mono-disperse sticky spheres collapse to form coexisting close-packed solid and infinitely dilute gases. We show that polydisperse sticky spheres also collapse and calculate the collapse temperature. The polydisperse spheres separate into fractions with narrower polydispersities which can then solidify. This is perhaps the first example of a single-peaked polydisperse mixture phase solidifying and separating. It implies that a mixture of polydisperse large hard spheres with much smaller hard spheres does not show fluid—fluid coexistence.     

Supertransferred hyperfine interaction in magnetic insulators (II)

The important mechanisms of supertransferred hyperfine (STHF) interactions in N–O–M chains are briefly discussed: (i) spin polarization ofns states in the N-ion due to the s-d exchange interaction,H _STHF ^sd ; (ii) contributions of spin-polarized states of the intervening O-ion,H _STHF ^II ; (iii) transfer of d-electrons of the M-ion to emptyns states in the N-ion,H _STHF ^III . The dependence ofH _STHF upon the N–O–M bond configuration, electronic structure, and orbital state of the M-ion is presented in a convenient form. The STHF interactions in the chains Sn⁴⁺–O^2––Fe³⁺, Cr³⁺ in compounds with slightly distorted Perovskite structure are considered. The STHF field in the chain Sn⁴⁺–O^2––Cr³⁺ is shown to change the sign within the range of angles near 170°. This conclusion is in line with published data on the isoelectronic chain Sn⁴⁺–O²–Mn⁴⁺ in the compounds Ca_1–x Sr _x MnO₃. The results obtained for the N–O–Fe³⁺ chain are rationalized by the predicted angular dependence ofH _STHF=+ cos + cos². Features of the STHF interactions in N–O–M chains with an M-ion in an orbital degenerate state are examplified by a preliminary analysis of N–O^2––V³⁺ chains in orthovanadites.     

Analytic solution of the Percus-Yevick equation for sticky hard sphere potential

It is shown that within the Percus-Yevick approximation the radial distribution function for sticky (i.e. with a surface adhesion) hard spheres satisfies a linear differential equation with retarded right-hand side. Using the theory of distributions and the Green's function technique the analytic solution of this equation is found and explicit formulas are given enabling one to evaluate the radial distribution function both for sticky and non-attractive hard spheres for any distance and any density.     

Magnetic and magnetotransport properties of Co-doped manganites with perovskite structure

A systematic study of the doping of the Mn-sites by cobalt in three series of manganites — La_0.76Ba_0.24(Mn_1−xCo_x)O₃ single crystals, La_2/3Ba_1/3(Mn_1−xCo_x)O₃ and La(Mn_1−xCo_x)O₃ ceramics has been performed. It was found that La(Mn_1−xCo_x)O₃ annealed at 800°C in the range 0.4x0.9 is a mixture of ferromagnetic domains with ordered Mn and Co ions and ionically disordered spin-glass domains. In the quenched samples the fraction of spin-glass-type component increases strongly. The La_2/3Ba_1/3(Mn_1−xCo_x)O₃ solid solutions exhibit also an evidence for phase separation in the range 0.5x0.8. All the La(Mn_1−xCo_x)O₃ samples show an insulating behavior, however, magnetoresistance reduces strongly when the cobalt content rises to x=0.5. The La_0.76Ba_0.24(Mn_1−xCo_x)O₃ single crystals show first-order phase transition below their Curie points associated with a change of ground state of the Co²⁺ ions. The magnetic phase diagrams are depicted. The results are discussed in terms of positive Mn³⁺–O–Mn⁴⁺, Mn³⁺–O–Mn³⁺, Mn⁴⁺–O–Co²⁺ and negative Mn⁴⁺–O–Mn⁴⁺, Co²⁺–O–Co²⁺, Co²⁺–O–Mn³⁺ superexchange interactions as well as Co²⁺ and Mn⁴⁺ ionic ordering.     

A turn-on fluorescent chemosensor for Hg based on phenanthroline fluorophore

Dipyrido[3,2-a:2′,3′-c]-phenazine (L) was employed as a selectively fluorescent chemosensor for Hg²⁺ in DMF solution under buffered conditions with its fluorescence being strongly increased. The fluorescence increasing was attributed to the formation of L–Hg²⁺ by 1:1 complex ratio (K=3.7×10⁵ M⁻¹), which constitutes the basis for the determination of Hg²⁺ with the prepared chemosensor. The experiment results also show that the response behavior of L to Hg²⁺ is pH independent in the range of pH 6.0–9.0 and show excellent sensitivity and selectivity for Hg²⁺ over other examined metal ions.     

Negative muon hyperfine transition rate in aluminum

The residual polarization of theF ^– hyperfine state of ^–27Al has been investigated as a function of applied transverse magnetic field strength using standard TD- ^–SR techniques. TheF ^– precession frequency is –0.2623(5) [theoretical value: –0.2622] times that of the free muon in the same field. The observed muon decay electron asymmetry in theF ^– state decreases with increasing magnetic field strength, due to initial precession in the opposite direction of theF ⁺ state, which most muon initially populate, followed by a rapid transition to theF ^– state. A fit of the data to this model indicates a transition rateR=41(9)s^–1, in good agreement with theoretical predictions. This method can be used to determineR experimentally in other cases where it is too fast to be observed directly.     

Visions: The coming revolutions in particle physics

We study the branching ratio, CP-violating asymmetry, forward-backward asymmetry and the CP-violating asymmetry in the forward-backward asymmetry for the exclusive decay B → Kτ⁺τ⁻ in the two Higgs doublet model with tree level flavor changing neutral currents (model III). We analyse the dependencies of these quantities on the neutral Higgs boson contributions and the CP parameter sinθ in the model III. We observe that to determine the neutral Higgs boson effects, the measurements of the forward-backward asymmetry and the CP-violating asymmetry in the forward-backward asymmetry for the decay B → Kτ⁺τ⁻ are promising.     

Electronic absorption in silicate mineral of copper

The electronic absorption spectrum of chrysocolla, a silicate mineral of copper, has been studied at room and liquid air temperatures. The observed bands were satisfactorily explained as belonging to Cu²⁺ ion subjected to tetragonal and spin-orbit fields. A good fit between the theoretical and observed band positions was obtained for the following crystal field parameters:Dq=–1400 cm^–1 Ds=–3000 cm^–1 Dt=–800 cm^–1 =–800 cm^–1     

Photophysics and Fluorimetric Titrations of Fluorescent Ion Indicators

A test based on time-resolved fluorescence experiments (Anal. Biochem. 245, 28–37, 1997) allows one to assess the interference of the excited-state association with the fluorimetric determination of the ground-state dissociation constant K _d of fluorescent ion:indicator complexes. If an inflection point occurs in the plot of the fluorescence signal vs – log[ion] in the ion concentration range where both decay times are invariant, this inflection point can be associated with the correct K _d. Here we apply this test to the fluorescent ion indicators SBFO (for Na⁺), Mag-fura-2 (for Mg²⁺), and APTRA-BTC (for Ca²⁺). In all three cases the decay times are invariant in the concentration ranges of the respective ions where the fluorescence titrations show unique inflection points, indicating that the fluorimetrically determined K _d values are the true K _d values.     

Optical properties of individual manganese-doped quantum dots

The magnetic state of a single magnetic ion (Mn²⁺) embedded in an individual quantum dot is optically probed using micro-spectroscopy. The fine structure of a confined exciton in the exchange field of a single Mn²⁺ ion (S=) is analyzed in detail. The exciton–Mn²⁺ exchange interaction shifts the energy of the exciton depending on the Mn²⁺ spin component and six emission lines are observed at zero magnetic field. The emission spectra of individual quantum dots containing a single magnetic Mn atom differ strongly from dot to dot. The differences are explained by the influence of the system geometry, specifically the in-plane asymmetry of the quantum dot and the position of the Mn atom. Depending on both these parameters, one has different characteristic emission features which either reveal or hide the spin state of the magnetic atom. The observed behavior in both zero field and under magnetic field can be explained quantitatively by the interplay between the exciton–Mn²⁺ exchange interaction (dependent on the Mn position) and the anisotropic part of the electron–hole exchange interaction (related to the asymmetry of the quantum dot).