Toward the Elucidation of the Competing Role of Evaporation and Thermal Decomposition in Ionic Liquids: A Multitechnique Study of the Vaporization Behavior of 1-Butyl-3-methylimidazolium Hexafluorophosphate under Effusion Conditions.

The evaporation/decomposition behavior of the imidazolium ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate (BMImPF6) was investigated in the overall temperature range 425-551 K by means of the molecular-effusion-based techniques Knudsen effusion mass loss (KEML) and Knudsen effusion mass spectrometry (KEMS), using effusion orifices of different size (from 0.2 to 3 mm in diameter). Specific effusion fluxes measured by KEML were found to depend markedly on the orifice size, suggesting the occurrence of a kinetically delayed evaporation/decomposition process. KEMS experiments revealed that other species are present in the vapor phase besides the intact ion pair BMImPF6(g) produced by the simple evaporation BMImPF6(l) = BMImPF6(g), with relative abundances depending on the orifice size-the larger the orifice, the larger the contribution of the BMImPF6(g) species. By combining KEML and KEMS results, the conclusion is drawn that in the investigated temperature range, when small effusion orifices are used, a significant part of the mass loss/volatility of BMImPF6 is due to molecular products formed by decomposition/dissociation processes rather than to evaporated intact ion pairs. Additional experiments performed by nonisothermal thermogravimetry-differential thermal analysis (TG-DTA) further support the evidence of simultaneous evaporation/decomposition, although the conventional decomposition temperature derived from TG curves is much higher than the temperatures covered in effusion experiments. Partial pressures of the BMImPF6(g) species were derived from KEMS spectra and analyzed by second- and third-law methods giving a value of ΔevapH298K° = 145.3 ± 2.9 kJ·mol-1 for the standard evaporation enthalpy of BMImPF6. A comparison is done with the behavior of the 1-butyl-3-methylimidazolium bis(trifluoromethyl)sulfonylimide (BMImNTf2) ionic liquid.

Examen Doppler de la insuficiencia venosa de miembros inferiores: consenso entre especialistas / Doppler examination of lower limb venous insufficiency: consensus among specialists

Se logró un consenso entre especialistas del Diagnóstico por Imágenes y cirujanos flebólogos en el protocolo de realización de los estudios Doppler para la insuficiencia venosa de miembros inferiores (MMII), incluyendo un acuerdo sobre la fisiopatología de la enfermedad, la nomenclatura y diámetros de los vasos que componen los distintos sistemas venosos y los parámetros Doppler a utilizar en la confección del informe de los estudios. Se realizó una reunión entre 6 cirujanos vasculares y 10 especialistas en Diagnóstico por Imágenes, donde se discutieron los distintos ítems planteados. Además, durante el encuentro se realizaron dos estudios Doppler de miembros inferiores a manera de ejemplo y se elaboró un documento preliminar con los puntos acordados. El resultado de este encuentro multidisciplinario es el punto de partida para comenzar a manejar una terminología común que permita mejorar el diagnóstico y la conducta terapéutica de esta patología

A consensus among Diagnostic Imaging specialists and vascular surgeons on a protocol for carrying out Doppler studies for lower limb venous insufficiency is presented. This includes an agreement on the pathophysiology of the disease, the nomenclature and vessel diameters that make up the different venous systems, as well as the Doppler parameters to be used in the for reporting the studies. A meeting was held with 6 vascular surgeons and 10 imaging specialists in which these different items were discussed. Two Doppler studies of the lower limbs were performed during this meeting as an example, and a draft document was prepared on the points agreed

The antimony-group 11 chemical bond: dissociation energies of the diatomic molecules CuSb, AgSb, and AuSb.

The intermetallic molecules CuSb, AgSb, and AuSb were identified in the effusive molecular beam produced at high temperature under equilibrium conditions in a double-cell-like Knudsen source. Several gaseous equilibria involving these species were studied by mass spectrometry as a function of temperature in the overall range 1349-1822 K, and the strength of the chemical bond formed between antimony and the group 11 metals was for the first time measured deriving the following thermochemical dissociation energies (D°(0), kJ/mol): 186.7 ± 5.1 (CuSb), 156.3 ± 4.9 (AgSb), 241.3 ± 5.8 (AuSb). The three species were also investigated computationally at the coupled cluster level with single, double, and noniterative quasiperturbative triple excitations (CCSD(T)). The spectroscopic parameters were calculated from the potential energy curves and the dissociation energies were evaluated at the Complete Basis Set limit, resulting in an overall good agreement with experimental values. An approximate evaluation of the spin-orbit effect was also performed. CCSD(T) calculations were further extended to the corresponding group 11 arsenide species which are here studied for the first time and the following dissociation energies (D°(0), kJ/mol): 190 ± 10 (CuAs), 151 ± 10 (AgAs), 240 ± 15 (AuAs) are proposed. Taking advantage of the new experimental and computational information here presented, the bond energy trends along group 11 and 4th and 5th periods of the periodic table were analyzed and the bond energies of the diatomic species CuBi and AuBi, yet experimentally unobserved, were predicted on an empirical basis.

The uncertain bond energy of the NaAu molecule: experimental redetermination and coupled cluster calculations.

The dissociation energy of the intermetallic molecule NaAu, for which two largely at variance experimental values are available in the literature, has been redetermined by the Knudsen effusion mass spectrometry method. The molecule has been produced in the vapor phase by a specially designed experimental setting inspired by the double oven technique. The equilibrium of dissociation to atoms as well as the exchange equilibrium with the gold dimer were monitored mass-spectrometrically over about a 600 K temperature range. The third-law analysis of the equilibrium data provides the dissociation energy D0° (NaAu, g) = 245.3 ± 6.8 kJ/mol, corresponding to a formation enthalpy at 298 K of 228.3 ± 7.5 kJ/mol. The NaAu species was also studied computationally at the CCSD(T) level with basis sets of increasing zeta quality thus allowing to evaluate the molecular parameters and the dissociation energy at the complete basis set limit.

Experimental and computational investigation of the group 11-group 2 diatomic molecules: first determination of the AuSr and AuBa bond energies and thermodynamic stability of the copper- and silver-alkaline earth species.

The dissociation energies of the intermetallic molecules AuSr and AuBa were for the first time determined by the Knudsen effusion mass spectrometry method. The two species were produced in the vapor phase equilibrated with apt mixtures of the constituent elements, and the dissociation equilibria were monitored mass-spectrometrically in the temperature range 1406-1971 K (AuSr) and 1505-1971 K (AuBa). The third-law analysis of the equilibrium data gives the following dissociation energies (D(0)°, in kJ/mol): 244.4 ± 4.8 (AuSr) and 273.3 ± 6.3 (AuBa), so completing the series of D(0)°s for the AuAE (AE = group 2 element) diatomics. The AuAE species were also studied computationally at the coupled cluster including single, double and perturbative triple excitation [CCSD(T)] level with basis sets of increasing zeta quality, and various complete basis set limit extrapolations were performed to calculate the dissociation energies. Furthermore, the entire series of the heteronuclear diatomic species formed from one group 11 (Cu, Ag) and one group 2 (Be, Mg, Ca, Sr, Ba) metal was studied by DFT with the hybrid meta-GGA TPSSh functional and the def2-QZVPP basis set, selected after screening a number of functional-basis set combinations using the AuAE species as benchmark. Dissociation energies, internuclear distances, vibrational frequencies, and anharmonic constants were determined for the CuAE and AgAE species and their thermal functions evaluated therefrom. On this basis, a thermodynamic evaluation of the formation of these species was carried out under various conditions.

Study of the fundamental units of novel semiconductor materials: structures, energetics, and thermodynamics of the Ge-Sn and Si-Ge-Sn molecular systems.

The binary Ge(y)Sn(z) and ternary Si(x)Ge(y)Sn(z) molecular systems containing up to five atoms were investigated by means of density functional theory and coupled cluster calculations. The minimum energy structures were calculated and higher energy isomers are also proposed. The atomization energies of the ground state isomers were calculated by the CCSD(T) method with correlation consistent basis sets up to quadruple-ζ quality. The resulting values were extrapolated to the complete basis set limit and corrected by an approximate evaluation of the spin-orbit effect. Energetic properties such as binding, fragmentation and mixing energies, and HOMO-LUMO gap were analyzed as a function of the cluster size and composition. By using empirically adjusted atomization energies and DFT harmonic frequencies, the thermal functions were evaluated, and a thermodynamic database for the Si-Ge-Sn system was built, containing data for 55 gaseous species. On this basis, equilibrium calculations were performed in the temperature interval 1600-2200 K aimed at predicting the composition of the gas phase under various conditions. The results presented here can be of interest to improve the microscopic knowledge of Ge-Sn and Si-Ge-Sn materials, which are among the most promising candidates for advanced applications in the field of electronic and optoelectronic components, both as epitaxially grown layers and as nanocrystal quantum dots.

The dissociation energy of the new diatomic molecules SiPb and GePb.

The diatomic molecules SiPb and GePb were for the first time identified by producing high temperature vapors of the constituent pure elements in a "double-oven-like" molecular-effusion assembly. The partial pressures of the atomic, heteronuclear, and homonuclear gaseous species observed in the vapor, namely, Si, Ge, Pb, SiPb, GePb, Pb2, Gen, and Sin (n=2-3), were mass-spectrometrically measured in the overall temperature ranges 1753-1961 K (Ge-Pb) and 1992-2314 K (Si-Pb). The dissociation energies of the new species were determined by second- and third-law analyses of both the direct dissociation reactions and isomolecular exchange reactions involving homonuclear molecules. The selected values of the dissociation energies at 0 K (D0 degrees) are 165.1+/-7.3 and 141.6+/-6.9 kJ/mol, respectively, for SiPb and GePb, and the corresponding enthalpies of formation (DeltafH0 degrees) are 476.4+/-7.3 and 419.3+/-6.9 kJ/mol. The ionization efficiency curves of the two species were measured, giving the following values for the first ionization energies: 7.0+/-0.2 eV (SiPb) and 7.1+/-0.2 eV (GePb). A computational study of the species SiPb and GePb was also carried out at the CCSD(T) level of theory using the relativistic electron core potential approach. Molecular parameters, adiabatic ionization energies, adiabatic electron affinities, and dissociation energies of the title species were calculated, as well as the enthalpy changes of the exchange reactions involving the other Pb-containing diatomics of group 14. Finally, a comparison between the experimental and theoretical results is presented, and from a semiempirical correlation the unknown dissociation energies of the SiSn and PbC molecules are predicted as 234+/-7 and 185+/-11 kJ/mol, respectively.

Energetics and thermodynamic stability of the mixed valence ytterbium germanides.

The results of an experimental study concerning the thermodynamic stability of the Yb germanides, described as intermediate valence compounds, complemented by a computational investigation for the Yb3Ge5 compound are reported. These compounds belong to the rare earth (RE) tetrelides (tetrel = Si, Ge, i.e., group 14 elements), a class of intermetallic materials showing unusual and promising physical properties (giant magnetocaloric effect, magnetostriction, and magnetoresistence). The high-temperature decomposition reactions of the Yb-Ge intermediate phases were studied experimentally by means of the KEMS (Knudsen effusion mass spectrometry) and KEWL (Knudsen effusion weight loss) techniques. From the reaction enthalpies derived by measuring the Yb(g) decomposition pressures as a function of temperature, the heats of formation of five out of six of the intermediate phases in the Yb-Ge system were calculated. From the computational side, the stability of the Yb3Ge5(s) compound has been investigated by DFT-LCAO-B3LYP (density functional theory-linear combination of atomic orbitals-hybrid b3lyp exchange-correlation functional) first principles calculations deriving its equilibrium geometry and the enthalpy of formation at 0 K in relation to the intermediate valence state of Yb in the lattice.

Mass spectrometric investigation of gaseous YbH, YbO and YbOH molecules.

The high-temperature gaseous molecules YbH, YbO and YbOH have been identified and their thermochemistry investigated by the Knudsen effusion mass spectrometry technique coupled with a controlled pressure gas inlet system. Solid ytterbium monosilicide and disilicide samples were made to react in the Knudsen cell with H2(g) and H2(g)/O2(g); in these conditions, several gaseous species (Yb, YbO, YbH, YbOH, SiO, SiO2, H2O) were formed under equilibrium conditions. The temperature dependences of the partial pressures of the observed gaseous molecules were analyzed to derive the Yb--X bond energies (X = H, O, OH). Selected values are D0o(Yb--H) = 179.4 +/- 2.0 kJ mol(-1), D0o(Yb--O) = 384 +/- 10 mol(-1) and D0o(Yb--OH) = 322 +/- 12 kJ mol(-1), and Delta(at)H0o(YbOH) = 746 +/- 12 kJ mol(-1). Density functional theory (DFT) calculations were also performed. Experimental and computational results are discussed and compared to previous data when available. The SiO/SiO2 high-temperature gaseous equilibrium was also observed.

A mass spectrometric and density functional study of the intermetallic molecules AuBe, AuMg, and AuCa.

The intermetallic molecules AuBe and AuCa were identified by means of the Knudsen-Effusion Mass Spectrometry technique in the high-temperature vapors produced by vaporizing Au-Be-Ca alloys of proper composition. The gaseous equilibria AuBe(g)+Au(g)=Au(2)(g)+Be(g) and AuCa(g)+Au(g)=Au(2)(g)+Ca(g) were studied in the temperature ranges 1720-1841 K and 1669-1841 K, respectively, by monitoring the partial pressures of all the species involved. The equilibrium data were analyzed by the third-law method, obtaining for the first time the dissociation energy D(0) ( composite function) of the two intermetallic species: D(0) ( composite function)(AuBe)=234.0+/-4.0 kJ/mol; D(0) ( composite function)(AuCa)=246.7+/-4.0 kJ/mol. These values are significantly higher than the recently published D(0) ( composite function) of the species AuMg (175.4+/-2.7 kJ/mol). Furthermore, the ionization energies (IE) of AuBe, AuMg, and AuCa were obtained by measuring the electron impact ionization efficiency curves, IE(AuBe)=7.5+/-0.3 eV, IE(AuMg)=6.7+/-0.3 eV, and IE(AuCa)=5.5+/-0.3 eV. Theoretical calculations were also carried out for these species by density functional theory methods (PW91 and BP86) used in conjunction with Stuttgart relativistic effective core potentials. Both functionals were found to perform very well in reproducing experimental D(0) ( composite function), IE, and molecular parameters.