Molecular dynamics study on evaporation and condensation of n-dodecane at liquid-vapor phase equilibria

Molecular dynamics simulations are performed to study the evaporation and condensation of n-dodecane (C(12)H(26)) at temperatures in the range 400-600 K. A modified optimized potential for liquid simulation model is applied to take into account the Lennard-Jones, bond bending and torsion potentials with the bond length constrained. The equilibrium liquid-vapor n-dodecane interface thickness is predicted to be ~1.2-2.0 nm. It is shown that the molecular chains lie preferentially parallel to the interface in the liquid-vapor transition region. The predicted evaporation/condensation coefficient decreased from 0.9 to 0.3 when temperature increased from 400 to 600 K. These values can be used for the formulation of boundary conditions in the kinetic modeling of droplet heating and evaporation processes; they are noticeably different from those predicted by the transition state theory. We also present the typical molecular behaviors in the evaporation and condensation processes. The molecular exchange in condensation, typical for simple molecules, has never been observed for n-dodecane molecular chains.     

Low-dimensional compounds containing cyanido groups. XXI. Crystal structure, spectroscopic, thermal and magnetic properties of two polymorphous modifications of [Cu(men)2Pt(CN)4]n complex (men = N-methyl-1,2-diaminoethane)

Violet (1) and blue (2) polymorphous modifications of [Cu(men)₂Pt(CN)₄]_n (men = N-methyl-1,2-diaminoethane) have been prepared and investigated by IR and UV-vis spectroscopy, thermal analysis, measurement of magnetic data and X-ray structural analysis. Both modifications are formed by similar but differently packed zigzag chains, which consist of [Cu(men)₂]²⁺ moieties bridged by two trans arranged cyanido groups of [Pt(CN)₄]²⁻ units. The Cu(II) atoms in both structures are hexacoordinated by four nitrogen atoms in the equatorial plane from two molecules of bidentate men ligands with the average Cu-N(Me) and Cu-N(H₂) bond lengths of 2.046(8) and 2.008(8) Å, respectively, and by two nitrogen atoms from bridging cyanido groups in the axial positions at average distance of 2.50(7) Å. Broad nearly symmetric bands observed in the UV-vis spectra of 1 and 2 of ²B_1g → ²E_g transitions are consistent with a deformed octahedral coordination of the CuN₆ chromophoric groups. One and two ν(CN) absorption bands observed in the IR spectra of 1 and 2, respectively, are in agreement with different local symmetries of [Pt(CN)₄]²⁻ units and different Cu-N(cyanido) bond lengths in these polymorphs and are subject of discussion on the spectral-structural correlations in 1D compounds. The complexes are stable up to 238 °C when their two-stage thermal decompositions start and ending up with a mixture of CuO and metallic Pt as the most probable final thermal decomposition products. The temperature dependence of the magnetic susceptibility suggests the presence of a weak antiferromagnetic exchange coupling between Cu(II) atoms in 1, J/hc = −0.17 cm⁻¹ and in 2, J/hc = −1.3 cm⁻¹.     

Instability of nanostructures patterned in polystyrene under high electric field gradients

A nanolithography technique based on the lateral displacement of electrically biased AFM tip was developed for nanostructures formation of 30-100 nm in width and 1-10 nm in height in the polystyrene (PS) films. It was demonstrated that the nanostructures patterned in annealed PS films (90K Mw) show slow exponential relaxation between 55 and 265 h depending on their size. Relaxation of the nanostructures in non-annealed films usually occurred in minutes. It was observed that in the annealed samples a negative electric charge accumulated in the areas where the nanostructures formed while in the non-annealed samples only the positive charge in exposed areas was detected using the electric force microscopy. After 320 h of monitoring under the humidity maintained between 25 and 27% it was suggested that slow dynamical changes of the nanostructures can be attributed to the negative electric charge dissipation in the annealed samples.     

Quantum Wall Crossing in $${{\mathcal N}=2}$$ Gauge Theories

We study refined and motivic wall-crossing formulas in N=2{{\mathcal N}=2} supersymmetric gauge theories with SU(2) gauge group and N _f < 4 matter hypermultiplets in the fundamental representation. Such gauge theories provide an excellent testing ground for the conjecture that “refined = motivic.”     

Vortex Counting and Lagrangian 3-Manifolds

To every 3-manifold M one can associate a two-dimensional ${\mathcal{N}=(2, 2)}$ supersymmetric field theory by compactifying five-dimensional ${\mathcal{N}=2}$ super-Yang?CMills theory on M. This system naturally appears in the study of half-BPS surface operators in four-dimensional ${\mathcal{N}=2}$ gauge theories on one hand, and in the geometric approach to knot homologies, on the other. We study the relation between vortex counting in such two-dimensional ${\mathcal{N}=(2, 2)}$ supersymmetric field theories and the refined BPS invariants of the dual geometries. In certain cases, this counting can also be mapped to the computation of degenerate conformal blocks in two-dimensional CFT??s. Degenerate limits of vertex operators in CFT receive a simple interpretation via geometric transitions in BPS counting.     

Fullerene C<Subscript>70</Subscript> Triplet Zero-Field Splitting Parameters Revisited by Light-Induced EPR at Thermal Equilibrium

Continuous-wave (CW) electron paramagnetic resonance (EPR) and echo-detected (ED) EPR spectra of triplet state of fullerene C₇₀ in molecular glasses of decalin, o-terphenyl and toluene, and in polymethylmethacrylate polymer were obtained under continuous light illumination. Temperature was high enough so that the EPR spectra corresponded to thermal equilibrium between the spin sublevels. The comparison of CW EPR and ED EPR data has shown that pseudorotation in the ³C₇₀ frame does not remarkably affect deriving the zero-field splitting (ZFS) D and E parameters from the EPR spectra. ³C₇₀ EPR spectra were simulated at 77 K fairly well using the distribution of the ZFS D and E parameters. These distributions may be caused by the inhomogeneity of the glassy matrix surrounding, which affects the Jahn–Teller distortions of ³C₇₀ molecules (D-strain and E-strain).     

Electron field emission properties of highly dense carbon nanotube arrays

In this paper, we have studied field emission properties of highly dense arrays of multi-walled carbon nanotubes (CNTs) used as cathodes in diode-type field emission devices with a phosphor screen. For the high-density CNT emitters it is demonstrated that the emission sites are located on the CNT-cathode edges, which is direct experimental evidence of the ‘edge effect’. The results of computer simulations (using ‘ANSYS Electromagnetic’ software) are presented to confirm the experimental data and to analyze the effect of patterning on the electric field distribution for high-density CNT arrays. It is shown that selective-area removal of nanotubes in the arrays leads to the formation of additional edges characterized by the high field enhancement factor and enhanced emission from the CNT cathodes. In addition, scanning probe microscopy techniques are employed to examine surface properties of the high-density CNT arrays. For CNT arrays of ‘short’ nanotubes, the work function distribution over the sample surface is detected using a scanning Kelvin microscopy method.     

New hexanuclear group 11 pyrazolate complexes: synthesis and photophysical features

The treatment of 2,2'-di(1,2-pyrazol-3-yl)-1,1'-binaphthyl with two equivalents of appropriate monovalent group 11 precursors in the presence of a base leads to a complete exchange of the pyrazole NH protons with M(+) cations. Structural characterisation of the copper(I) complex revealed a hexanuclear complex with a pelton-wheel-like arrangement of the binaphthyl unit. As indicated by their spectroscopic data, all three complexes are isostructural. The complexes show a complex fluorescence behaviour that can be partially related to the ligand system and also to the metal sites, as indicated by the position of the fluorescence peaks and their temperature dependence and lifetimes.