A theoretical study of hemiacetal formation from the reaction of methanol with derivatives of CX3CHO (X = H,F, Cl,Br and I)

A theoretical study of the hemiacetal formation reaction between methanol and CX₃CHO (X = H, F, Cl, Br, and I) has been carried out using density functional theory and Becke, three‐parameter, Lee–Yang–Parr/6‐311++G(d,p) computational methods. The stationary points of the reaction between the isolated molecules and the reaction catalyzed by an additional methanol molecule have been characterized. Because the final products present a stereogenic center, the potential autocatalysis of the reaction has been examined and also the possibility of spontaneous generation of chirality when the hemiacetal molecules are involved in the transition state structure. High barriers are found in the reaction between the isolated molecules that are reduced by the assistance of an additional molecule (methanol or hemiacetal product). The reactions catalyzed by the hemiacetal products show higher barriers than the one catalyzed by methanol. Copyright © 2012 John Wiley & Sons, Ltd.     

Thermodynamically stable phases of carbon at multiterapascal pressures

Phases of carbon are studied up to pressures of 1 petapascal (PPa) using first-principles density-functional-theory methods and a structure searching algorithm. Our extensive search over the potential energy surface supports the sequence of transitions diamond → BC8 → simple cubic under increasing pressure found in previous theoretical studies. At higher pressures we predict a soft-phonon driven transition to a simple hexagonal structure at 6.4 terapascals (TPa), and further transitions to the face centered cubic electride structure at 21 TPa, a double hexagonal close packed structure at 270 TPa, and the body centered cubic structure at 650 TPa.     

Thermomolecular orientation of nonpolar fluids

We investigate the response of molecular fluids to temperature gradients. Using nonequilibrium molecular dynamics computer simulations we show that nonpolar diatomic fluids adopt a preferred orientation as a response to a temperature gradient. We find that the magnitude of this thermomolecular orientation effect is proportional to the strength of the temperature gradient and the degree of molecular anisotropy, as defined by the different size or mass of the molecular atomic sites. We show that the preferred orientation of the molecules follows the same trends observed in the Soret effect of binary mixtures. We argue this is a general effect that should be observed in a wide range of length scales.     

Synchronization in simple network motifs with negligible correlation and mutual information measures

Can different or even identical coupled oscillators be completely uncorrelated and still be synchronized? What can be concluded from the absence of correlations or even mutual information in networks of dynamical elements about their connectivity? These are fundamental and far-reaching questions arising in many complex systems. In this Letter, we address these two questions and demonstrate in simple and generic network motifs that synchronized behavior in the generalized sense can be realized and constructed such that no correlations and even negligible mutual information remain. Our findings raise new questions, in particular, whether and to what extent indirect connections are being underestimated, since the related collective behavior and even synchronization are less likely to be detected.     

Morphology and thermal stability of AlF3 thin films grown on Cu(100)

The growth of ultrathin epitaxial layers of aluminum fluoride on Cu(100) has been studied by a combination of surface science techniques. Deposition at room temperature results in step decoration followed by the formation of dendritic two-dimensional islands that coalesce to form porous films. Ultrathin layers (up to 2 monolayers in thickness) are morphologically unstable upon annealing; de-wetting takes place around 430 K with the formation of three-dimensional islands and leaving a large fraction of the Cu surface uncovered. Films several nanometers thick, on the contrary, are stable up to ca. 730 K where desorption in molecular form sets on. The effect of electron irradiation on the AlF₃ has also been characterized by different spectroscopic techniques; we find that even small quantities of stray electrons from rear electron beam heating can provoke significant decomposition of the aluminum fluoride, resulting in the release of molecular fluorine and the formation of deposits of metallic aluminum. These features make AlF₃ an interesting material for spintronic applications.     

Closed-form BER analysis of variable weight MPPM coding under gamma-gamma scintillation for atmospheric optical communications

In this paper, the performance of the variable weight multiple pulse-position modulation (MPPM) coding technique in an atmospheric optical communication environment under gamma-gamma optical scintillation is analyzed, proposing a closed-form expression for the average bit error rate (BER). This study is based on a hyperexponential fitting of the conditional BER in absence of turbulence fluctuations, leading to closed-form expressions that characterize the behavior of this nonlinear coding scheme. Finally, conditional and average BER expressions proposed here are corroborated with Monte Carlo simulations results.     

Theoretical study of the conformational energy hypersurface of cyclotrisarcosyl

The multidimensional Conformational Potential Energy Hypersurface (PEHS) of cyclotrisarcosyl was comprehensively investigated at the DFT (B3LYP/6-31G(d), B3LYP/6-31G(d,p) and B3LYP/6-311++G(d,p)), levels of theory. The equilibrium structures, their relative stability, and the Transition State (TS) structures involved in the conformational interconversion pathways were analyzed. Aug-cc-pVTZ//B3LYP/6-311++G(d,p) and MP2/6-31G(d)//B3LYP/6-311++G(d,p) single point calculations predict a symmetric cis-cis-cis crown conformation as the energetically preferred form for this compound, which is in agreement with the experimental data. The conformational interconversion between the global minimum and the twist form requires 20.88 kcal mol-1 at the MP2/6-31G(d)//B3LYP/6-311++G(d,p) level of theory. Our results allow us to form a concise idea about the internal intricacies of the PEHSs of this cyclic tripeptide, describing the conformations as well as the conformational interconversion processes in this hypersurface. In addition, a comparative analysis between the conformational behaviors of cyclotrisarcosyl with that previously reported for cyclotriglycine was carried out     

Diastereoselective indium-mediated allylation of N-tert-butanesulfinyl ketimines: easy access to asymmetric quaternary stereocenters bearing nitrogen atoms

Indium-mediated allylation of N-tert-butanesulfinyl ketimines afforded in high yields and diastereoselectivities homoallylic amine derivatives with the nitrogen atom bonded to a quaternary stereocenter.     

Nanoscale mapping of plasmon resonances of functional multibranched gold nanoparticles

The optical response of multibranched gold nanoparticles is studied by means of electron energy-loss spectroscopy (EELS) in aberration corrected STEM mode. In every case the plasmon response is constant and variations in the maxima positions were found to be dependent on the branches aspect ratio. The good spatial resolution combined with the high energy resolution (0.18 eV) of the monochromated electron beam allows mapping the different plasmonic modes along the entire nanoparticles ranging from 0.7 eV up to 2.25 eV.