Three-dimensional microfabrication by two-photon-initiated polymerization with a low-cost microlaser

Fabrication of submicrometer structures by two-photon-initiated polymerization is performed with an inexpensive and low-power microlaser. This is made possible by the design of photoinitiators with strong two-photon absorption cross sections. We analyze the influence of both material properties and irradiation conditions on the two-photon polymerization rate and show that resins based on our highly sensitive two-photon photoinitiator can be solidified with microlaser excitation, whereas commercial UV photoresins require ultrashort and intense laser pulses.     

Rotation spectrum and infrared fundamental bands of 123SbD3. Determination of molecular geometry and ab initio calculations of spectroscopic parameters

The high resolution infrared spectrum of ¹²³SbD₃ has been recorded in the 20–350?cm^?1 range and in the regions of the ν₁, ν₃ and ν₂, ν₄ fundamental bands centred at 1350 and 600?cm^?1, respectively. Splitting of the K′′?=?3, 6 lines have been observed both in the rotation and ro-vibration spectra. A large number of ‘perturbation allowed‘ transitions with selection rules Δ(k??l) =?±?3,?±?6, and?±?9 have been identified in all fundamental bands. Accurate ground state molecular parameters have been determined by means of a simultaneous fit of the rotational transitions and about 12?000 ground state combination differences from the infrared bands. The A and B reductions of the rotational Hamiltonian provided almost equivalent results. The molecular parameters of the ν _i ?=?1 (i?=?1???4) states were obtained as a result of the simultaneous analysis of the ν₁ (A₁)/ν₃ (E) stretching and of the ν₂ (A₁)/ν₄ (E) bending dyads. In fact, the corresponding excited states are affected by strong perturbations due to rovibrational interactions of Coriolis and k-type that have been treated explicitly in the model adopted for the analysis. Improved effective ground state and equilibrium geometries were determined for the molecule and compared to those of ¹²³SbH₃. Ab initio calculations at the coupled cluster CCSD(T) level with an energy-consistent large-core pseudopotential and large basis sets were carried out to determine the equilibrium structure, the anharmonic force field, and the associated spectroscopic constants of ¹²³SbH₃ and ¹²³SbD₃. The theoretical results are in good agreement with the experimental data.     

High oxygen pressures and the stabilization of six-coordinated Ir(VI) in an oxygen lattice

Abstract

During these last twenty five years a great efforts have been made in the Laboratoire de Chimie du Solide du CNRS in order to develop high oxygen pressure for the stabilization of unusual oxidation state of transition elements.

The aims of such research works was to correlate the increase of the Mⁿ⁺-O bond covalency versus the increase of the oxidation state n+ to the physicochemical properties of resulting oxides [1].

Iridium was an interesting element due to its position (5d) in the Periodic Table. In 1980 Ir(V) (d⁴) was stabilized in La₂LiIrO₆ in the perovskite structure [2]. Such a study had underlined the strong value of the spin-orbit coupling associated to Ir(V) [3].

The stabilization of Ir(VI) is interesting from two points of view : (i) its isotropic electronic configuration (d³), (ii) such a high oxidation state could lead to the strongest M-O bond in an oxygen lattice.

Selecting, through a specific methodology, the most appropriate local structural and chemical factors and with the help of high oxygen pressure, Ir(V1) was stabilized in the perovskite Ba₂CaIrO₆. Structural, magnetic and Mössbauer studies have been carried out in order to characterize the physicochemical properties induced by this unusual oxidation state.     

Dynamics and non-equilibrium steady state in a system of coupled harmonic oscillators

A system of two coupled oscillators, each of them coupled to an independent reservoir, is analysed. The analytical solution of the non-rotating wave master equation is obtained in the high-temperature and weak coupling limits. No thermal entanglement is found in the high-temperature limit. In the weak coupling limit the system converges to an entangled non-equilibrium steady state. A critical temperature for the appearance of quantum correlations is found.     

Benchmark values for the Soret,thermal diffusion and diffusion coefficients of three binary organic liquid mixtures

With the aim of providing reliable benchmark values, we have measured the Soret, diffusion and thermal diffusion coefficients of the three binary mixtures of dodecane, isobutylbenzene and 1,2,3,4 tetrahydronaphthalene for a concentration of 50 wt% at a temperature of 25C. The experimental techniques applied by the five participating laboratories are transient holographic gratings, annular and parallelepipedic thermogravitational columns, and vertical parallelepipedic columns with velocity amplitude determination by laser doppler velocimetry. The systems have also been studied in a annular thermogravitational column filled with a porous medium in the gap. There is a good agreement between the different experiments with deviations of the order of a few per cent in most cases (8.5% at most). The numerical values are tabulated in the paper.     

Effect of gas pressure and pulse length on the isotopically selective multiphoton dissociation of CF3Cl under CO2 laser pulses

The multiphoton dissociation of CF₃Cl induced by TEA-CO₂ laser pulses has been studied in a focused beam geometry. TheR(10) [00°1–02°0] ( ) laser line was used, so as to dissociate preferentially the minor isotopic component¹³CF₃Cl. The isotopic selectivityS and the dissociation probability per pulse ω were measured in the pressure range between 0.25 and 8 Torr. With short laser pulses (90 ns FWHM),S is found to increase slightly with gas pressure up to 2 Torr, and ω, to increase almost linearly over the whole pressure range studied. A schematic model is proposed which satisfactorily explains these results if the transition rates across the energy level spectrum of the CF₃Cl molecules are assumed to increase with gas pressure.     

Production of vector and tensor mesons in proton-proton collisions at\sqrt s = 52.5 GeV

Inclusive production of ?⁰,f, andg ⁰ mesons and ofK _s ⁰ ,K ^*0 (892), ? andK ^*0(1430)mesons has been measured at <y>～2.6 and <p _T >～1.1 GeV/c in proton-proton interactions at \(\sqrt s = 52.5\) GeV. The negative particle from the two-body decays of these resonances were identified by a threshold Cerenkov counter and used for triggering. Starting from the measured differential cross section, total inclusive cross sections for the vector and tensor mesons were determined using various parametrizations for they andp _T dependence of the differential cross section. The experimental results are discussed in the framework of production models based on the parton picture. The strangeness suppresion factor λ=(0.30±0.10) due toSU(3) symmetry breaking of the quark sea is derived.     

Diffusion approximations for the scattering of resonance-line photons: Interior and boundary layer solutions

Resonance-line scattering in static low density media with large optical thickness has a diffusive behavior in both space and frequency because photons belonging to the Lorentzian wings of the line may be scattered almost monochromatically a very large number of times. This diffusive behavior holds on frequency scales and spatial scales, χ_c and τ_c, much larger than the scales associated with one elementary scattering of a wing-photon.A method developed for diffusion approximations in neutron transport theory, suitably generalized to handle diffusion in frequency space, is applied to the case of conservative scattering in a bounded medium with interior sources and zero incoming radiation. The method is to separate the line radiation field into an interior part and a boundary layer part which goes to zero in the interior. Each part is expanded in terms of a small parameter ?, which is the ratio of the mean free-path at frequency χ_c to the characteristic spatial scale τ_c.It is shown that the leading term in the interior asymptotic expansion is isotropic, zero on the boundary, and obeys a space and frequency diffusion equation. In the boundary-layer expansion, the leading term is of order ? and is a solution to a monochromatic transfer equation in a semi-infinite, plane-parallel medium. The emergent radiation field is shown to be of order ? and proportional to the gradient of the interior solution at the boundary. Its angular dependence, in the case of isotropic scattering in the atom frame, is given by the Ambartsoumian H-function. A comparison is presented between numerical solutions of the full transfer equation and asymptotic solutions. Non-conservative scattering and time-dependent problems are briefly discussed.     

Systematic trends in the237neptunium Mössbauer isomer shift: Overlap of IV,V and VI neptunium oxidation states and correlation between isomer shift and crystal structure

The influence of the neptunium ion environment on the²³⁷Np Mössbauer isomer shifts has been studied in various metal coordination complexes: fluorides, oxides, oxide fluorides and polycarboxylates. A linear dependence between the isomer shift and the mean neptunium-ligand distance in a series of hexavalent Np compounds has been evidenced and the feasibility of overlapped isomer shift areas, namely Np(IV), Np(V) and Np(VI) has been established.