Activities and thermodynamic excess properties of aqueous 2,5-dimethylpyridine mixtures near the critical demixing point: Comparison with 2,6-dimethylpyridine-water mixtures

Activities of 2,5-dimethylpyridine in aqueous solution have been measured at eleven temperatures, two below and nine above the lower critical temperature of the mixture, by the dynamic method of Randall and Weber. Gibbs free energy, enthalpy and entropy are derived to obtain excess quantities and all the results are discussed in connection with the liquid-liquid phase separation, the critical situation and the association properties of the molecules. A comparison is also made with the aqueous 2,6-dimethylpyridine system. A new version of the phase diagram is proposed.     

Towards minimal assumptions for the infimal convolution regularization

We encompass the Moreau-Yosida regularization process by infimal convolution into a general framework. This sheds light on the assumptions required for obtaining the usual properties. In particular the class of lower-T² mappings is shown to be a suitable class for performing the usual proximal regularization in open subsets of Hilbert spaces. The role of growth conditions is pointed out.     

Analysis of the high resolution spectrum of the fundamental bandsv2 andv5 of12CH3F and their interactions

Thev ₂(A₁) andv ⁵(E) fundamental vibration-rotation bands of¹²CH₃F have been recorded under high resolution (0.015 to 0.020 cm^–1) in the spectral range of 1460 cm^–1. About 1100 transitions have been assigned. The Coriolis interaction between v₂=1 and v₅=1, and the l(2,-1) interaction in v₅=1 have been rigorously treated. Sixteen molecular constants have been determined from a least squares analysis. They reproduce the observed data with an overall standard deviation of 0.0037 cm^–1.     

Synthesis and two-photon absorption of triphenylbenzene-cored dendritic chromophores

The synthesis and the characterization of triphenylbenzene-cored dendrimers of first- and second-generation are described. Their absorption, photoluminescence as well as their two-photon absorption properties have been investigated and compared to a quadrupolar counterpart. These molecules combine wide transparency in the visible range and high two-photon absorption cross-sections that increase with the generation, making these dendrimers promising systems for optical power limiting applications.     

Synthesis and two-photon absorption of highly soluble three-branched fluorenylene-vinylene derivatives

Two new three-branched fluorenylene-vinylene derivatives were synthesized by triple Heck-type or Horner-Wadsworth-Emmons reactions. Their one-photon absorption and fluorescence as well as their two-photon absorption properties are reported. These compounds, which combine very high solubility in organic solvents, high fluorescence quantum yield and giant two-photon absorption cross-sections in the red-NIR region (up to 3660 GM, in the femtosecond regime) are promising candidates for both optical power limiting applications and two-photon laser scanning microscopy.     

Gadolinium and neodymium citrates: evidence for weak ferromagnetic exchange between gadolinium(III) cations

A new lanthanide citrate motif of general formula [Ln(Hcit)(H2O)2.H2O]n, where Ln = Gd (1) and Nd (2) and Hcit3- = C(OH)(COO-)(CH2COO-)2, has been synthesized hydrothermally from Ln2O3 and citric acid at 100 degrees C and characterized by elemental analysis, IR, TG-DTA, single-crystal X-ray diffraction, and magnetic measurements. The structures can be seen as "ladder chains" along the a axis, with dinuclear Ln2O2 units serving as "steps" and R-COO groups as "uprights", which are connected by H bonds. The magnetic susceptibility between 2 and 300 K and the magnetization at 2 K, as a function of magnetic field between 0 and 5 T, were measured for both compounds. By modeling the magnetic behavior of the Gd compound with a dinuclear Hamiltonian [symbol: see text](S) = gmu(B)(S(A) + S(B))B(o) - J(o)S(A)S(B) (S(A) = S(B) = 7/2), a ferromagnetic exchange interaction J(o) = 0.039 cm(-1) was evaluated between Gd ions situated at d(o) = 4.321 angstroms in dinuclear units bridged by two symmetry-related tridentate carboxylate oxygens. The EPR spectrum of the Gd compound is discussed. The temperature dependence of the susceptibility of the Nd compound is caused by the depopulation of the excited crystal-field levels when the temperature decreases. The magnetic-field dependence of the magnetization of 2 is attributed to the ground-state Kramers' doublet populated at 2 K. The g factor of this ground-state doublet is calculated from the data and compared with values for other compounds reported in the literature.     

Diaroyl(methanato)boron difluoride compounds as medium-sensitive two-photon fluorescent probes

This paper evaluates the use of diaroyl(methanato)boron difluoride compounds for designing efficient fluorescent probes through two-photon absorption. Three different pathways allowing for the syntheses of symmetrical and dissymmetrical molecules are reported. The stable diaroyl(methanato)boron difluoride derivatives can be easily obtained in good yields. They exhibit a large one-photon absorption that is easily tuned in the near-UV range. Their strong fluorescence emission covers the whole visible domain. In addition to these attractive linear properties, several diaroyl(methanato)boron difluoride derivatives possess significant cross sections for two-photon absorption. The derived structure-property relationships are promising for designing new generations of molecules relying on the diaroyl(methanato)boron difluoride backbone.     

Variation–iteration method in momentum space: Determination of Hartree–Fock atomic orbitals

A method using the Svartholm iterative procedure to solve atomic Hartree–Fock equations in momentum space is defined and applied to the ground states of Be and B⁺. The calculated atomic orbital properties follow a monotonic and stable convergence, but with rates of convergence depending on each property. The evolution of the orbitals during the iterations is explained by the combined actions of the variational principle, the Svartholm iterative procedure, and the momentum space representation. © 1993 John Wiley & Sons, Inc.