Molecular dynamics of liquid acetone determined by depolarized Rayleigh and low-frequency Raman scattering spectroscopy

Slow to ultrafast dynamics of liquid acetone at variable temperature was investigated by depolarized Rayleigh and low-frequency Raman scattering spectroscopy, in the region 0-200 cm(-1). A detailed analysis was performed on the spectra and corresponding time responses, and a consistent view of the molecular dynamics of this dipolar solvent was obtained. The effects of temperature on the spectra were interpreted, and distinct dynamical processes identified. At very low frequencies, or long time scales, acetone dynamics is characterized by a slow diffusive reorientation obeying the Stokes-Einstein-Debye hydrodynamic theory only in the limit of subslip boundary conditions. An alternative model based on the microviscosity concept proved to be able to reproduce this correlation time and its temperature dependence. A comparative analysis of collective and single-molecule reorientational times, these latter estimated from intramolecular Raman spectra, led to an orientational correlation parameter g(2) of unity, which denotes a statistical disorder of molecular polarizability tensors. A fast local restructuring process is putatively responsible for an additional contribution at subpicosecond time scales often referred to as intermediate response in other molecular liquids. The high frequency portion of the dynamical susceptibility showed the signature of librational intermolecular motions, giving rise to an ultrafast decay of the time correlation function of polarizability anisotropy. The overall approach, which provided valuable information on dynamics, structure and molecular interactions of neat acetone, will be applied to acetone electrolytic solutions.     

A mixed algorithm for the calculation of rapidly varying fluid flows: The impulsively started circular cylinder

A mixed discrete Fourier transform-Finite difference algorithm is developed and used for the calculation of rapidly changing viscous fluid flows past a circular cylinder. The numerical approach has been designed to overcome certain difficulties arising for high Reynolds number simulations. The foremost advantage of the technique lies in its fast calculations of the convolution sums portraying the convective terms of the governing equations. Third-order spatial discretizations and fourth-order time marching are implemented. New schemes are proposed for the boundary conditions at the solid wall and at large distances. The techniques are tested on a case study with other schemes (summarized by Roache¹) in order to obtain an optimal choice. Definite indications on the stability and accuracy of boundary condition schemes are achieved. Support for the statement of dominant importance of boundary conditions is also given. A comparison of computational results with experimental data is presented for the case study of the flow past an impulsively started cylinder at Reynolds number 20. The time development of the symmetrical zone of recirculation, which is formed at an early stage of the flow, has been studied for 300 ≤ Re ≤ 9500 by means of the proposed algorithm. Computational results, comparisons with experimental data² and discussion of upper limits of validity of the procedure will be presented in a companion paper.     

Released momentum distribution of a Fermi gas in the BCS-BEC crossover

We develop a time-dependent mean-field theory to investigate the released momentum distribution and the released energy of an ultracold Fermi gas in the BCS-BEC crossover after the scattering length has been set to zero by a fast magnetic-field ramp. For a homogeneous gas we analyze the nonequilibrium dynamics of the system as a function of the interaction strength and of the ramp speed. For a trapped gas the theoretical predictions are compared with experimental results.     

Critical temperature of interacting Bose gases in two and three dimensions

We calculate the superfluid transition temperature of homogeneous interacting Bose gases in three and two spatial dimensions using large-scale path integral Monte Carlo simulations (with up to N=10;{5} particles). In 3D we investigate the limits of the universal critical behavior in terms of the scattering length alone by using different models for the interatomic potential. We find that this type of universality sets in at small values of the gas parameter na3 < or approximately 10(-4). This value is different from the estimate na3 < or approximately 10(-6) for the validity of the asymptotic expansion in the limit of vanishing na3. In 2D we study the Berezinskii-Kosterlitz-Thouless transition of a gas with hard-core interactions. For this system we find good agreement with the classical lattice |psi|4 model up to very large densities. We also explain the origin of the existing discrepancy between previous studies of the same problem.     

Crystal structure of the complex between 7,7,8,8-tetracyanoquinodimethane and 1-oxide-2-phenyl-quinoline

A series of complexes between 1-oxide quinolines and 7,7,8,8-tetracyanoquinodimethane has been synthesized and one of them has been analyzed by x-ray diffraction methods. Crystals of the title compound are monoclinic (C₁₅H₁₁NO·C₁₂H₄N₄), space groupP2₁/n,a=44.525(4),b=7.326(2),c=6.531(2) Å,=90.23(3)°. The structure was solved by direct methods and refined by block-matrix least-squares to giveR=0.047 for 1865 reflections above 2(I). Molecular dimensions, interplanar distances, empirical method and IR spectra suggest a -^* interaction with very low charge-transfer in the complex.     

Antibacterial activity of a new class of tris homoleptic Ru (II)-complexes with alkyl-tetrazoles as diimine-type ligands

Herein, we describe a new family of tris chelate homoleptic Ru (II) complexes, [Ru(N^N) ₃ ] ²⁺ , where the role of the diimine-type ligands (N^N) was fulfilled by 2-pyridyl (PTZ) or 2-quinolyl tetrazole (QTZ) derivatives decorated with various alkyl substituents at the N-2 position of the tetrazole ring. The new Ru (II) complexes with general formula [Ru (PTZ-R) ₃ ] ²⁺ and [Ru (QTZ-R) ₃ ] ²⁺ , were obtained as mixtures of facial (fac) and meridional (mer) isomers, as suggested by NMR (¹H, ¹³C) experiments, and confirmed in the case of mer-[Ru (QTZ-Me) ₃ ] ²⁺ , by X-ray crystallography. The photophysical behavior of the tetrazole-based [Ru(N^N) ₃ ] ²⁺ type species was investigated by UV–vis absorption spectroscopy, providing trends typical of polypyridyl Ru (II) complexes. The new homoleptic complexes fac/mer- [Ru (PTZ-R) ₃ ] ²⁺ and fac/mer- [Ru (QTZ-R) ₃ ] ²⁺ have been assessed for any eventual antimicrobial activity towards two different bacteria such as Gram-negative Escherichia coli and Gram-positive Deinococcus radiodurans. Whereas being inactive toward E. coli, the response of agar disks diffusion tests suggested that some of the new fac/mer Ru (II) complexes could inhibit the growth of D. radiodurans. This effect was further investigated by determining the growth kinetics in liquid medium of D. radiodurans exposed to the fac/mer- [Ru (PTZ-R) ₃ ] ²⁺ and fac/mer- [Ru (QTZ-R) ₃ ] ²⁺ complexes at different concentrations. The outcome of these experiments highlighted that the turn-on of the growth inhibitory effect took place as the linear hexyl chain was appended to the PTZ or QTZ scaffold, suggesting also how the inhibitory activity appeared more pronouncedly exerted by the facial isomers fac- [Ru (PTZ-Hex) ₃ ] ²⁺ and fac- [Ru (QTZ-Hex) ₃ ] ²⁺ (MIC = ca. 3.0 μg/ml) with respect to the corresponding meridional isomers (MIC = ca. 6.0 μg/ml).     

Molecular associations of [2.2]paracyclophanearylhydrazones with organic acceptors,VIII

Summary Molecular complexes of mono and disubstituted [2.2]paracyclophanehydrazones with organic acceptors have been studied by means of thermodynamic and spectroscopic properties. Furthermore, the enhancement of the donor strength, induced by the hydrazono group, is viewed in the light of substituent as well as transannular effects.

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Molekulare Assoziation von [2.2]Paracyclophanarylhydrazonen mit organischen Akzeptoren, 8. Mitt.

Zusammenfassung Es wurden Molekülkomplexe von mono- und disubstituierten [2.2]Paracyclophanarylhydrazonen mit organischen Akzeptoren mittels thermodynamischer und spektroskopischer Methoden untersucht. Zusätzlich wird der Anstieg in der Donorstärke, der von der Hydrazonogruppe induziert wird, im Hinblick auf Substituenten- und auch transannulare Effekte diskutiert.

     

Complexes of azobisindoles with π-organic acceptors

Complexes of azobisindoles with tetracyanoethylene and tetracyanoquinodimethane were studied by UV-Vis, FT-IR, Raman, NMR and X-ray spectroscopies. FT-IR and Raman spectra, as well as X-ray analysis, gave useful information on the participation of various sites to the association, through analysis of CN and N=N vibrational modes, while UV-Vis and NMR spectra were less helpful. The crystal structure of complexes 1-ethyl-2-phenyl-3-(1-ethyl-2-phenyl-3-azoindole)indole/TCNE,3a and 1,2-diphenyl-3-(1,2-diphenyl-3-azoindole)indole/TCNQ,5b are reported. In the two complexes, the distances between donor and acceptor planes range between 3.4 and 3.5 Å; in3a tetracyanoethylene faces the phenyl ring of the indole, while in5b the superposition of tetracyanoquinodimethane with the donor is negligible. Compound3a,P–1,a=9.504(2),b=9.513(3),c=8.941(2) Å, =97.81(4), =103.38(3), =84.14(2)°,Z=2,D _calc=2.55 g cm^–3; compound5b,P–1,a=12.648(3),b=12.205(2),c=7.263(3) Å, =103.69(2), =91.23(3), =110.61(2)°,Z=2,D _calc=2.53 g cm^–3.