Buckling in a solid Langmuir monolayer: light scattering measurements and elastic model

Above a surface pressure threshold , we detect a buckled state in the low temperature solid phase of a phospholipid monolayer spread at the air-formamide interface. Stable ripples are observed with a Brewster angle microscope, and light scattering provides measurements mNm^-1, wavelength m and amplitude of a few nm for the deformation. A model, coupling the monolayer thickness and elongation, and consistent with the monolayer texture, is also presented. Received: 18 August 1997 / Revised: 9 December 1997 / Accepted: 29 January 1998     

Proximity effect in Fe/Pb/Fe trilayers

We have studied superconducting and magnetic properties of sputtered Fe/Pb/Fe-trilayers. For a fixed Pb thickness and with changing Fe thickness, , a monotonic decrease of the superconducting transition temperature was observed. Magnetization measurements clearly showed that Fe remains ferromagnetic down to the monolayer range. A quantitative comparison of with the theory of pair breaking by the exchange field reveals that the observed -suppression by the ferromagnetic Fe-layer is much weaker than expected. Possible reasons for the reduced -suppression in this system are discussed. Received: 30 June 1997 / Revised: 20 August 1997 / Accepted: 16 December 1997     

Transfer of smectic films to a solid substrate by the method of Maclennan

We investigate monolayers of 2-alcohols (2-C9 to 2-C16) obtained by placing a drop of pure alcohol at the water surface. These alcohols are chiral molecules and we study the racemic mixtures. By ellipsometry and surface tension measurements we are able to characterize the 2D crystallization-melting transition with temperature. We find a first order transition. Using X-ray under grazing incidence we show that the racemic mixture crystallizes at 2D on a hexagonal cell. We find a parity effect on the lateral pressure at the transition and on the stability of the Bragg peak. We compare all results with those observed for 1-alcohols. Received: 11 April 1997 / Revised: 18 August 1997 / Accepted: 9 October 1997     

Rotational effects in low energy dissociative recombination of diatomic ions

The effect of rotational interaction in the low energy dissociative recombination process of diatomic molecules has been explored for typical molecular ions () which sample a large range of molecular masses. We show that rotation plays a role mainly for the indirect recombination process through bound Rydberg states, and for light molecules. When the direct process based on a strong electronic interaction is fast and dominating, rotational couplings can be safely neglected especially for heavier molecules like NO. Received: 18 September 1997 / Revised in final form: 17 October 1997 / Accepted: 20 October 1997     

Inelastic neutron scattering from H2 on vapour deposited CO2

Inelastic neutron scattering spectra at 17 meV and 68 meV incident energies of molecular hydrogen adsorbed on vapour deposited substrates of pure CO₂, 90:10 and 50:50 CO₂:Kr are reported. The ortho-para transition is shifted from 14.7 meV in the free H₂-molecule to 9.4 meV in a presumably commensurate ortho-H₂ monolayer on the CO₂ surface. The quadrupole-quadrupole interaction of ortho-H₂ molecules with the CO₂ substrate results in a strongly anisotropic potential. In addition to rotations the dynamics of this layer comprise a local Einstein mode and phonons in resonance with the substrate, giving rise to intense multiphonon transitions. Quasielastic scattering on warmer samples is assigned to a liquidlike adsorption layer, in which the H₂ rotations are strongly perturbed. Received: 15 October 1996 / Revised: 25 August 1997 / Accepted: 24 October 1997     

Reverse self-assembly: (111)-oriented gold crystallization at alkylthiol monolayer templates

It has long been known that thiol-terminated molecules self-assemble as commensurate monolayers on Au(111) surfaces. By spreading floating octadecanethiol monolayers on aqueous solutions of chloroauric acid (HAuCl4) and using x rays to reduce the gold ions as well as to probe the structure, we have observed the nucleation of (111)-oriented Au nanoparticles at thiol surfaces. This process may be similar to the formation of biogenic gold by bacteria. The thiol monolayer acts as a "soft template," changing its structure as Au crystals form so that there is a sqrt[3]×sqrt[3] commensurate relationship.     

Probing the diffusion of vacuum ultraviolet (λ = 172 nm) induced oxidants by nanoparticles immobilization

Vacuum ultraviolet (VUV, λ = 172 nm) patterning of alkyl monolayer on silicon surface has been demonstrated with emphasis on the diffusion of VUV induced oxygen-derived active species, which are accountable for the pattern broadening. The VUV photons photo-dissociates the atmospheric oxygen and water molecules into the oxygen-derived active species (oxidants). These oxidants photo-oxidize the hexadecyl (HD) monolayer in VUV irradiated regions (Khatri et al., Langmuir. 24 (2008) 12077), as well as the little concentration of oxidants diffuses towards the masked areas. In this study, we performed VUV patterning at a vacuum pressure of 10 Pa to track the diffusion pathways for the oxidants with help of gold nanoparticles (AuNPs; ? = 10 nm) immobilization. At VUV irradiated sites AuNPs are found as uniformly distributed, but adjacent to the pattern boundary we observed quasi-linear arrays of AuNPs, which are determined by diffusion pathways of the oxidants. The diffusion of oxidants plays vital role in pattern broadening. The site selective anchoring of AuNPs demonstrates the utility of VUV photons for the construction of functional materials with microstructural architecture.     

Mn-site doping induced CMR properties in calcium rich manganites Pr1‒xCaxMnO3(0.6 ≤ x ≤ 0.7)

Doping of Mn-site by chromium, cobalt and nickel has been investigated in the calcium rich manganites and . Whatever the nature of the doping element, a rapid disappearance of the charge ordered (CO) state is observed, decreasing as the doping rate increases. But the most important result concerns the Cr-doped compounds for which a re-entrant insulator to metal transition at 90-120 K is observed for x =0.10-0.12, in a zero magnetic field. The possibility to induce colossal magnetoresistance (CMR) properties for high (IV) contents ((IV)/) for x =0.07-0.12 is shown for the first time, the resistance ratios reaching at 30 K. This study also shows differently that the small size of the A-site cation (Pr, Ca) is not a redhibitory obstacle to the appearance of CMR properties in manganites, in contrast with previously established phase diagrams. Received: 18 June 1997 / Revised: 4 August 1997 / Accepted: 10 November 1997     

Nuclear fusion in charge-asymmetric muonic molecules

Nuclear fusion reactions in hydrogen-lithium muonic molecules, (where h=p,d,t) are considered and fusion rates from rotational states J=0 of the molecules are presented. Results obtained depend on the isotopic composition of the molecules and range between and . The upper limit for fusion rates from rotational states J=0 of hydrogen-helium muonic molecules, and , equal , is also found. Received: 4 December 1997 / Revised: 30 April 1998 / Accepted: 7 May 1998     

Shape anisotropy and magnetic domain structures in striped monolayers

We study the effect of dipolar interactions on a magnetic striped monolayer with a microscopic unit cell of square symmetry, and of size spins. Even if the aspect ratio r=N _x /N _y is very large, an in-plane shape anisotropy is always negligible, except if N_y is fairly small (N _y <40). In-plane domains are not possible, except for values of the dipolar coupling larger than the domain wall energy. Received: 11 July 1997 / Revised: 24 September 1997 / Accepted: 24 October 1997     

A scenario for the electronic state in the manganese perovskites: the orbital correlated metal

We propose a novel scenario for the electronic state in the manganese perovskites. We argue that, at low temperatures and within the ferromagnetic state, the physics of these colossal magnetoresistance compounds may be characterized by a correlated metallic state near a metal insulator transition where the orbital degrees of freedom play the main role. This follows from the observation that a two-band degenerate Hubbard model under a strong magnetic field can be mapped onto a para-orbital single band model. We solve the model numerically using the quantum Monte-Carlo technique within a dynamical mean field theory which is exact in the limit of large lattice connectivity. We argue that the proposed scenario may allow for the qualitative interpretation of a variety of experiments which were also observed in other (early) transition metal oxides. Received: 3 October 1997 / Revised: 9 December 1997 / Accepted: 12 January 1998     

Microscopic measurement of the linear compressibilities of two-dimensional fatty acid mesophases

The linear compressibility of two-dimensional fatty acid mesophases has been determined by grazing incidence X-ray diffraction. The unit cell parameters of the , , , S and phases of behenic acid and of the phase of myristic acid were determined as a function of surface pressure and temperature. Surface pressure versus molecular area isotherms were reconstructed from these measurements, and the linear compressibility (relative distortion along a given direction for a two-dimensional isotropic applied stress) was determined both in the sample plane and in a plane normal to the aliphatic chain director (transverse plane). The linear compressibilities range over two orders of magnitude from 0.1 to 10 m/N and are distributed depending on their magnitude in 4 different sets which we are able to associate with different molecular mechanisms. The largest compressibilities (10 m/N) are observed in the tilted phases. They are apparently independent on the chain length and could be related to the reorganization of the headgroup hydrogen-bounded network, whose role should be revalued. Intermediate compressibilities are observed in phases with quasi long-range order (directions normal to the molecular tilt in the or phases, S phase, and could be related to the ordering of these phases. The lowest compressibilities are observed in the solid untilted phase and for one direction of the S and phases. They are similar to the compressibility of crystalline polymers and correspond to the interactions between methyl groups in the crystal. Finally, negative compressibilities are observed in the transverse plane for the and phases and can be traced to subtle reorganizations upon untilting. Received: 29 July 1997 / Revised: 14 October 1997 / Accepted: 23 October 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     

Coherent population transfer in NO with pulsed lasers: the consequences of hyperfine structure, doppler broadening aaand electromagnetically induced absorption

Coherent population transfer between vibrational levels of the NO molecule induced by the interaction of two delayed laser pulses, also referred to as stimulated Raman scattering involving adiabatic passage (STIRAP), is studied experimentally in a molecular beam and in the bulk. The consequences of hyperfine splitting and Doppler broadening are discussed in detail. Unlike in previous studies of this kind, transfer occurs simultaneously between more than one group of non degenerate levels. In a molecular beam or in the bulk, the transfer efficiency of STIRAP exceeds that obtained by Stimulated Emission Pumping (SEP) by a factor of 3.6 or 15, respectively. We estimate the absolute transfer efficiency T in the beam to be , while is found in the bulk. In both cases, this is of the maximum value expected from numerical studies. Possible reasons for this discrepancy are discussed. Finally we show that the absorption of a pump pulse in a weakly absorbing medium is significantly enhanced by the presence of a copropagating Stokes pulse when the Rabi frequency of the latter is smaller than the width of the Doppler profile . The relation of this observation to the phenomenon of Electromagnetically Induced Transparency (EIT), which is observed for , is also discussed. Received: 11 September 1997 / Revised: 28 October 1997 / Accepted: 29 October 1997     

Ethanol and methanol induced changes in phospholipid monolayer

The main components of cell membranes are phospholipids and proteins. The aim of our study was to examine structural changes of dipalmitoyl-phosphatidylcholine (DPPC) monolayer as a simple model system of a cell membrane in different environments. Pure water, ethanol and methanol solutions were used as subphases of Langmuir films as a membrane models. For detection of changes in charge states of the molecules as well as relation with structural and conformational changes, a contactless method Maxwell's displacement currents (MDC) was used. Behaviour of DPPC molecules on two different subphases is substantialy different. In DPPC monolayer on the subphase of methanol-water, a gradual absorption (incorporation, penetration) of methanol molecules into the layer can appear. In DPPC monolayer on the subphase of ethanol-water adsorption of ethanol molecules on the layer can be observed. The membrane permeability might change. At both subphases (ethanol-water and methanol-water) the elasticity modulus of the monolayer decreases leading to the loss of membrane elasticity.     

Influence of molecular adsorbate layers on the optical spectra of small metal particles

2 , N₂O, CO₂ or N₂ on the particle surface. Depending on the molecules to which the clusters are exposed, different changes of the surface plasmon resonance in the spectra can be identified. The most essential experimental results are as follows. First, changes of the optical spectra are found if the clusters are covered by less than a molecular monolayer. Secondly, the observed variations of the spectra allow to distinguish between physisorption and chemisorption, i.e. characterize the strength of the surface chemical bond. Third, in sharp contrast to the usual shift of the plasmon frequency to longer wavelengths by change of the dielectric surrounding, a blue shift of the resonance has been observed upon dosage of CO₂. Finally, diffusion of adsorbate molecules into the bulk of the particles can be identified. Received: 11 September 1997     

Evolution from BCS superconductivity to Bose condensation: analytic results for the crossover in three dimensions

We provide an analytic solution for the mean-field equations and for the relevant physical quantities at the Gaussian level, in terms of the complete elliptic integrals of the first and second kinds, for the crossover problem from BCS superconductivity to Bose-Einstein condensation of a three-dimensional system of free fermions interacting via an attractive contact potential at zero temperature. This analytic solution enables us to follow the evolution between the two limits in a particularly simple and transparent way, as well as to verify the absence of singularities during the evolution. Received: 9 May 1997 / Revised: 4 August 1997 / Accepted: 6 November 1997     

A phenomenology of boundary lubrication: the lumped junction model

We propose a phenomenological model of boundary lubricated junctions consisting of a few layers of small molecules which describes the rheological properties of these sytems both in the static, frozen, and sliding, molten, states as well as the dynamical transition between them. Two dynamical regimes can be distinguished, according to the level of internal damping of the junction, which depends on its thickness and on the normal load. In the overdamped regime, under driving at constant velocity v through an external spring, the motion evolves continuously from “atomic stick-slip” to modulated sliding. Underdamped systems exhibit, under given external stress, a range of dynamic bistability where the sheared static state coexists with a steadily sliding one. The frictional dynamics under shear driving is analyzed in detail, it provides a complete account of the qualitative dynamical scenarios observed by Israelashvili et al., and yields semiquantitative agreement with experimental data. A few complementary experimental tests of the model are suggested. Received: 18 December 1997 / Received in final form and accepted: 26 March 1998     

Concerning the first-order phase transition in the low-dimensional organic superconductor (BEDO—TTF)2ReO4 · H2O. Crystal and electronic band structures below the phase transition (T = 170 K)

The effect of the first-order phase transition occurring around 220 K on the crystal and electronic structure of the molecular superconductor (BEDO-TTF) has been studied. The crystal structure at 170 K has been determined and it is found that the main structural change resulting from the phase transition is connected with a rotation of the anions. This rotation leads to changes in the SS and SO intermolecular contacts within the BEDO-TTF donor layers. How these structural changes affect the electronic structure of the salt is studied by comparing the transfer integrals for the different donordonor intermolecular interactions calculated for the room temperature and 170 K crystal structures. It is shown that Fermi surfaces for the 170 K and room temperature structures are very similar, do not exhibit nesting properties, and can be described as resulting from the hybridization of superposing ellipses. Received: 4 September 1997 / Received in final form: 2 December 1997 / Accepted: 3 December 1997