All spin-2 cubic vertices with two derivatives

In this paper we provide a complete list of spin-2 cubic interaction vertices with two derivatives. We work in (anti) de Sitter space with dimension d?4$d?4$ and arbitrary value of cosmological constante and use simple metric formalism without any auxiliary or Stueckelberg fields. We separately consider cases with one, two and three different spin-2 fields entering the vertex where each field may be massive, massless or partially massless one. The connection of our results with massive (bi)gravity theories is also briefly discussed.     

Resistivity of a non-galilean-invariant Fermi liquid near Pomeranchuk quantum criticality

We analyze the effect of the electron-electron interaction on the resistivity of a metal near a Pomeranchuk quantum phase transition (QPT). We show that umklapp processes are not effective near a QPT, and one must consider both interactions and disorder to obtain a finite and T dependent resistivity. By power counting, the correction to the residual resistivity at low T scales as AT((D+2)/3) near a Z=3 QPT. We show, however, that A=0 for a simply connected, convex Fermi surface in 2D, due to the hidden integrability of the electron motion. We argue that A>0 in a two-band (s-d) model and propose this model as an explanation for the observed T((D+2)/3) behavior.     

Luminescence of metal surface due to nonequilibrium excitation of electrons by laser radiation

Laser-induced nonequilibrium electromagnetic radiation (NEMR) from the surface of metal target has been observed. NEMR has a high temperature and can't be explained by means of usual heating of surface by laser radiation. This phenomenon is connected with the “hot” electron emission and can be described in terms of physical kinetics.     

Fire eruption through intensity and spread rate interaction mediated by flow attachment

Conditions under which a fire has a stable steady spread rate or under which it is able to spread eruptively up a slope or in confined topography are of considerable interest from a practical and safety point of view. The physical interactions that give rise to either form of behaviour are investigated by way of a mathematical model, in which different expressions for the rate of feedback from intensity into spread-rate are found to identify a threshold between eruptive and stable spread of a line fire. In turn, changes in the fireline intensity in any unsteady evolution are mainly determined by the history of the spread-rate over a burnout time (in effect, by changes in flame depth). Under stable conditions, any initial spread-rate evolves towards the steady spread rate on a time-scale of the order of the burnout time. But above the threshold, eruptive fire-growth sets in; the spread-rate and intensity both grow indefinitely.

It is argued that a change in the nature of the flow field around a line fire engenders the change from one form of behaviour to another. If the air flow separates at the flame, so that air is drawn away from the ground and vegetation surface, then the model provides strong reasons to expect that the steady spread rate is stable. On the other hand, laboratory experiments and a controlled field burn confirm that eruptive behaviour is more likely to be associated with flow attachment.

As a result, if the air immediately ahead of a fire that is spreading uphill, flows up the slope away from the fire then conditions arise for a potentially very dangerous acceleration in the spread-rate of the fire, along with a corresponding growth in its intensity. As is shown by the experiments, this form of air-flow can be generated by the fire itself without any change in external conditions such as ambient wind.     

π‐Extended Indenofluorenes

A series of π‐extended aromatic indenofluorene (IF) analogues with naphthalene and anthracene cores have been synthesized through acid‐catalyzed intramolecular cyclization. The regioselectivity of the reaction is controlled by a combination of steric and electronic factors and in some cases several possible regioisomers have resulted from the same precursor. The effects of ring connectivity on the optoelectronic properties were investigated by DFT calculations, absorption/emission spectroscopy, cyclic voltammetry, and spectroelectrochemical studies. All regioisomers exhibited a redshift of their absorption/emission bands relative to the parent IF analogues, but the magnitude of this shift and other optoelectronic properties (luminescence quantum yield, etc.) depends on the ring connectivity in a less obvious manner.     

Multidimensional scaling and visualization of large molecular similarity tables

Multidimensional scaling (MDS) is a collection of statistical techniques that attempt to embed a set of patterns described by means of a dissimilarity matrix into a low‐dimensional display plane in a way that preserves their original pairwise interrelationships as closely as possible. Unfortunately, current MDS algorithms are notoriously slow, and their use is limited to small data sets. In this article, we present a family of algorithms that combine nonlinear mapping techniques with neural networks, and make possible the scaling of very large data sets that are intractable with conventional methodologies. The method employs a nonlinear mapping algorithm to project a small random sample, and then “learns” the underlying transform using one or more multilayer perceptrons. The distinct advantage of this approach is that it captures the nonlinear mapping relationship in an explicit function, and allows the scaling of additional patterns as they become available, without the need to reconstruct the entire map. A novel encoding scheme is described, allowing this methodology to be used with a wide variety of input data representations and similarity functions. The potential of the algorithm is illustrated in the analysis of two combinatorial libraries and an ensemble of molecular conformations. The method is particularly useful for extracting low‐dimensional Cartesian coordinate vectors from large binary spaces, such as those encountered in the analysis of large chemical data sets. © 2001 John Wiley & Sons, Inc. J Comput Chem 22: 488–500, 2001     

The rate constant of polymer reversal inside a pore

Translocation of biopolymers through pores is implicated in many biological phenomena. Confinement within a pore often breaks ergodicity on experimental and/or biological time scales by creating large entropic barriers to conformational rearrangements of the chain. Here, we study one example of such hindered rearrangement, in which the chain reverses its direction inside a long pore. Our goal is twofold. First, we study the dependence of the time scale of polymer reversal on the pore size and on the polymer length. Second, we examine the ability of simple one-dimensional theories to quantitatively describe a transition in a system with a complex energy landscape by comparing them with the exact rate constant obtained using brute-force simulations and the forward flux sampling method. We find that one-dimensional transition state theory (TST) using the polymer extension along the pore axis as the reaction coordinate adequately accounts for the exponentially strong dependence of the reversal rate constant on the pore radius r and the polymer length N, while the transmission factor, i.e., the ratio of the exact rate and the TST approximation, has a much weaker power law r and N dependence. We have further attempted to estimate the transmission factor from Kramer's theory, which assumes the reaction coordinate dynamics to be governed by a Langevin equation. However, such an approximation was found to be inadequate. Finally, we examine the scaling behavior of the reversal rate constant with N and r and show that finite size effects are important even for chains with N up to several hundreds.     

New chiral lanthanide amide ate complexes for the catalysed synthesis of scalemic nitrogen-containing heterocycles

New chiral binaphthylamido yttrium and ytterbium ate complexes with lithium and potassium counterions have been synthesised and characterised. X-ray structures have been obtained for [Li(thf)4][Ln{(R)-C20H12(NC5H9)2}2] (Ln=Yb, Y) and [K(thf)5][Yb{(R)-C20H12(NCH2CMe3)2}2] as isostructural complexes. The efficiency of these complexes for the enantioselective intramolecular hydroamination was examined. [Li(thf)4][Yb{(R)-C20H12(NC5H9)2}2] afforded the highest enantiomeric excess (up to 87 %) for the synthesis of a spiropyrrolidine, while [Li(thf)4][Y{(R)-C20H12(NC5H9)2}2] proved to be slightly more active. The role of the counter cation in the active catalytic species was evidenced by the comparison between lithium and potassium ate complexes. The most active catalyst of this series, [Li(thf)4][Yb{(R)-C20H12(NCH2CMe3)2}2], was successfully used for the cyclisation of aminopentenes with internal double bonds.     

Halogen bonds as stabilizing interactions in a chiral self-assembled molecular monolayer

We report the formation of highly-ordered self-assembled monolayers of an achiral organic semiconductor molecule. STM results show spontaneous formation of very large single domains of ordered chiral monolayers. DFT calculations support the identification of halogen bonds as the primary interactions that steer molecular self-assembly, leading to organizational chirality.