On the Second Law of Thermodynamics and the Piston Problem

The piston problem is investigated in the case where the length of the cylinder is infinite (on both sides) and the ratio m/M is a very small parameter, where m is the mass of one particle of the gaz and M is the mass of the piston. Introducing initial conditions such that the stochastic motion of the piston remains in the average at the origin (no drift), it is shown that the time evolution of the fluids, analytically derived from Liouville equation in a previous work, agrees with the Second Law of thermodynamics. We thus have a non equilibrium microscopical model whose evolution can be explicitly shown to obey the two laws of thermodynamics.     

Catalytic Hydrosilylation of Furan, Thiophene, and Pyridine Aldimines

The addition of hydrosilanes (HSiEt₃, HSiMe₂Ph, H₂SiPh₂) to the CH=N bond of heterocyclic azomethines has been studied in the presence of monovalent complexes of rhodium and palladium. The effect on the reaction of the CF₃ group of the aldimines, which were obtained from O-, S-, and N-heteroaromatic aldehydes and 2-trifluoromethylaniline, has been clarified, as were other regularities of the processes being studied. A series of corresponding furans, thiophenes, and pyridine amines has been synthesized.     

Trace cocharacters and the Kronecker products of Schur functions

It follows from the theory of trace identities developed by Procesi and Razmyslov that the trace cocharacters arising from the trace identities of the algebra M_r(F) of r×r matrices over a field F of characteristic zero are given by TC_r,n=∑_λΛr(n)χ^λχ^λ where χ^λχ^λ denotes the Kronecker product of the irreducible characters of the symmetric group associated with the partition λ with itself and Λ_r(n) denotes the set of partitions of n with r or fewer parts, i.e. the set of partitions λ=(λ₁λ_k) with kr. We study the behavior of the sequence of trace cocharacters TC_r,n. In particular, we study the behavior of the coefficient of χ^(ν,n−m) in TC_r,n as a function of n where ν=(ν₁ν_k) is some fixed partition of m and n−mν_k. Our main result shows that such coefficients always grow as a polynomial in n of degree r−1.     

Spreading Code Design Using a Global Optimization Method

The performance of a code division multiple access system depends on the correlation properties of the employed spreading code. Low cross-correlation values between spreading sequences are desired to suppress multiple access interference and to improve bit error performance. An auto-correlation function with a distinct peak enables proper synchronization and suppresses intersymbol interference. However, these requirements contradict each other and a trade-off needs to be established. In this paper, a global two dimensional optimization method is proposed to minimize the out-of-phase average mean-square aperiodic auto-correlation with average mean-square aperiodic cross-correlation being allowed to lie within a fixed region. This approach is applied to design sets of complex spreading sequences. A design example is presented to illustrate the relation between various correlation characteristics. The correlations of the obtained sets are compared with correlations of other known sequences.     

Measurement of the dynamic elastic constants of short isotropic cylinders

A method based on a single test is proposed to characterize the elasticity of an isotropic homogeneous material in the shape of a cylinder of any slenderness (length-diameter) ratio. Firstly, the Rayleigh-Ritz method is used to determine the natural frequencies of the cylinders vibrating axisymmetrically. The study is focused on cylindrical samples with diameter and length of similar magnitude so that the shear modulus and the Poisson ratio can be calculated simultaneously. Subsequently, the theoretical results for cylinders of slenderness ratio between 0.1 and 3 are analyzed in order to obtain the data required to determine the elastic constants from one of the two lowest measured natural frequencies and their quotient. The analysis of the results demonstrates that any slenderness ratio is useful in the calculation of the elastic constants, although in some cases the third natural frequency should be used. Furthermore, the influence of the length-diameter quotient on the sensitivity of the method is analyzed by evaluating the systematic uncertainties for both dynamic elastic constants. Finally, the method is experimentally tested by characterizing two steel cylinders with slenderness ratios 0.1 and 1, respectively. The results demonstrate that uncertainties for both Poisson ratio and the shear modulus are smaller when the slenderness ratio is 1.     

Braids on surfaces and finite type invariants

We prove that there is no functorial universal finite type invariant for braids in Σ×I if the genus of Σ is positive. To cite this article: P. Bellingeri, L. Funar, C. R. Acad. Sci. Paris, Ser. I 338 (2004).     

Une axiomatisation de la substitution

We investigate the notion of substitution in an abstract way, without defining it explicitly. We single out the essential features of the operation of performing a substitution in order to define a concept of substitutive structure, called logos. We then prove a completeness theorem making precise and justifying the intuition that formulas true for the usual substitution can be proved from the logos axioms only. To cite this article: M. Crabbé, C. R. Acad. Sci. Paris, Ser. I 338 (2004).     

Charge transfer excitons: dynamic theory of vibronic spectra

The vibronic spectra of charge transfer excitons (CTE) in a molecular one-component or alternatingly ordered two-component chain are treated in the framework of a dynamic approach (neglecting thermal excitations of the intramolecular vibrations). The model introduces two mechanisms of coupling between CTEs and vibrational quanta: (1) shift of the equilibrium positions of the nuclei in the ionized donor or acceptor; (2) change of the vibrational frequency in the ionized molecule. This model allows to generalize the simple CTE Hamiltonian and the vibronic Hamiltonian of Frenkel excitons. The linear optical susceptibility is calculated in the vibronic region (one CTE and one vibrational quantum). The double splitting of vibronics of CTEs was analyzed: (1) the splitting connected with the location of the intramolecular vibration on the donors or on the acceptors; (2) the splitting connected with the symmetry of the vibronic spectra (in the degenerate case). The general structure of the vibronic spectra of CTEs is established. It contains structureless absorption lines, which correspond to two-particle bands (the phonon is excited on a neutral molecule neighboring the donor or the acceptor) and Lorentz-type lines of one-particle states, which correspond to the bound propagation of the CTE and the phonon.     

Ar-Broadening of isotropic Raman lines in the ν2 band of acetylene

Using a high resolution Raman spectrometer, we have measured Ar-broadening coefficients in the ν₂Q branch of C₂H₂ for 22 lines at 295 K, 20 lines at 174 K, and 16 lines at 134 K. These lines with J values ranging from 1 to 23 are located in the spectral range 1970.9-1974.3 cm⁻¹. The collisional widths are obtained by fitting each spectral line with a Rautian profile. The resulting broadening coefficients are compared with theoretical values arising from close coupling and coupled states calculations. A satisfactory agreement is obtained at room as well as at low temperatures, especially for odd J lines. By comparing broadening coefficients at 295, 174, and 134 K from a simple power law, the temperature dependence of these broadenings has been determined both experimentally, and theoretically.     

Rotational spectra, conformational structures, and dipole moments of thiodiglycol by jet-cooled FTMW and ab initio calculations

The rotational spectra of three low-energy conformers of thiodiglycol (TDG) (HOCH₂CH₂SCH₂CH₂OH) have been measured in a molecular beam using a pulsed-nozzle Fourier-transform microwave spectrometer. To determine the likely conformational structures with ab initio approach, conformational structures of 2-(ethylthio)ethanol (HOEES) (CH₃CH₂SCH₂CH₂OH) were used as starting points together with the consideration of possible intramolecular hydrogen bonding in TDG. Three lower-energy conformers have been found for TDG at the MP2=Full/6311G** level and ab initio results agree nicely with experimentally determined rotational constants. In addition, Stark measurements were performed for two of the three conformers for dipole moment determinations, adding to our confidence of the conformational structure matches between experimental observations and ab initio calculations. Of the three lower-energy conformers, one displays a compact folded-like structure with strong hydrogen bonding between the two hydroxyl groups and the central sulfide atom. Two other conformers have relatively open chain-like structures with hydrogen bonding between each of the hydroxyl groups to the central sulfur atom, of which one has pure b-type dipole moment according to the ab initio results.