Conductance switching in diarylethenes bridging carbon nanotubes

The recently reported photoswitching of diarylethene derivative molecules bridging carbon nanotube (CNT) contacts is theoretically analyzed. The short lifetime of the lowest unoccupied molecular orbital (LUMO) indicates that neither the open nor closed form of the molecule can be photoexcited into a charge-neutral excited state for any appreciable length of time preventing photochromic ring opening. Analysis of the highest occupied molecular orbital (HOMO) and LUMO lifetimes also suggests that photoexcitation results in oxidation of the molecules. This either reduces the quantum yield of photochromic ring closing, or it gives rise to the possibility of oxidative ring closing. Analysis of the resistance values and energy levels indicates that the HOMO energy levels of the closed isomers relevant for transport must lie within a few k(B)T of the CNT Fermi level. For armchair contacts, the change in resistance with isomer or substituent group is the result of shifts in the energy level of the molecular HOMO. The coupling of the molecular HOMO to the CNT contacts is insensitive to the isomer type or substituent group. For zigzag CNTs, the conductance is dominated by surface states at the Fermi level on the cut ends of the CNTs so that the conductance is relatively insensitive to the isomer type, and the conductance switching ratio is low. Multiple bridging molecules can interact coherently, resulting in energy splitting, shifting, and interference that cause a nonlinear change in conductance with increasing numbers of molecules. Instead of a factor of 3 increase in conductance expected for three independent channels, a factor of 10(3) increase in conductance is obtained for three bridging molecules.     

Role of wing morphing in thrust generation

In this paper, we investigate the role of morphing on flight dynamics of two birds by simulating the flow over rigid and morphing wings that have the characteristics of two different birds, namely the Giant Petrel and Dove Prion. The simulation of a flapping rigid wing shows that the root of the wing should be placed at a specific angle of attack in order to generate enough lift to balance the weight of the bird. However, in this case the generated thrust is either very small, or even negative, depending on the wing shape. Further, results show that morphing of the wing enables a significant increase in the thrust and propulsive efficiency. This indicates that the birds actually utilize some sort of active wing twisting and bending to produce enough thrust. This study should facilitate better guidance for the design of flapping air vehicles.     

On nonparametric ridge estimation for multivariate long-memory processes

Lithuanian Mathematical Journal - We consider nonparametric estimation of the ridge of a probability density function for multivariate linear processes with long-range dependence. We derive...     

Second-order correction to perfect pairing: an inexpensive electronic structure method for the treatment of strong electron-electron correlations

We have formulated a second-order perturbative correction for perfect-pairing wave functions [PP2] based on similarity-transformed perturbation techniques in coupled cluster theory. The perfect-pairing approximation is used to obtain a simple reference wave function which can qualitatively describe bond breaking, diradicals, and other highly correlated systems, and the perturbative correction accounts for the dynamical correlation. An efficient implementation of this correction using the resolution of the identity approximation enables PP2 to be computed at a cost only a few times larger than that of canonical MP2 for systems with hundreds of active electrons and tens of heavy atoms. PP2 significantly improves on MP2 predictions in various systems with a challenging electronic structure.     

Quantum chemical study of oxygen adsorption on graphite: I. Molecular orbital study of adsorption and migration of molecular oxygen on graphite

Possible stable Van der Waals complexes of molecular oxygen on the surface of graphite modelled by 16 C and 10 H atoms were investigated by the method based on the Buckingham potential. The CNDO/2 calculations of potential curves of chemisorption of oxygen molecule on graphite were used to determine the adsorption heat on different surface sites. The migration of molecular oxygen on the surface of graphite was examined by means of energy contour maps. Also, the influence of preadsorbed oxygen on the chemisorption of the oxygen molecule was studied.     

A New Method of the Preparation of Imido‐bis(sulfuric acid) Dihalogenide, (F,Cl), and the Potassium Salt of Imido‐bis(sulfuric acid) Difluoride

The article describes a new and effective synthesis of pure imido‐bis(sulfuric acid) dihalogenides (halogenide = F, Cl) and the potassium salt of imido‐bis(sulfuric acid) difluoride, KN(SO₂F)₂.     

Pulse propagation of acoustic waves scattered in a channel

When acoustic waves are scattered by random sound-speed fluctuations in a two-dimensional channel the energy is continually transferred between the propagating modes. In the multiple- scattering region the energy flux assumes an asymptotic form in which there is equal energy flux propagating in each mode. Here we shall make use of this well known result to show how to obtain an asymptotic form for a pulse of acoustic energy propagating in the channel. In the multiple-scattering region the speed of the acoustic waves in the pulse continually changes as the energy is transferred between the modes. The process is basically a diffusion process around the mean speed of propagation. We shall first show, using physical arguments, that the diffusion coefficient is proportional to the square root of the propagation distance times the mean free path of scattering. The theory governing the acoustic propagation in the channel is formulated in terms of modal coherence equations and we shall next give a brief review of the definitions of the coherence functions and a discussion of how the equations governing the propagation of the modal coherence functions are derived. We shall then show how the pulse shape and the relevant parameters may be obtained by solving the basic modal coherence equations at large propagation distances.     

Modeling Small Structural and Environmental Differences in Solids with 15N NMR Chemical Shift Tensors

The ability to theoretically predict accurate NMR chemical shifts in solids is increasingly important due to the role such shifts play in selecting among proposed model structures. Herein, two theoretical methods are evaluated for their ability to assign ¹⁵N shifts from guanosine dihydrate to one of the two independent molecules present in the lattice. The NMR data consist of ¹⁵N shift tensors from 10 resonances. Analysis using periodic boundary or fragment methods consider a benchmark dataset to estimate errors and predict uncertainties of 5.6 and 6.2 ppm, respectively. Despite this high accuracy, only one of the five sites were confidently assigned to a specific molecule of the asymmetric unit. This limitation is not due to negligible differences in experimental data, as most sites exhibit differences of >6.0 ppm between pairs of resonances representing a given position. Instead, the theoretical methods are insufficiently accurate to make assignments at most positions.     

Testing for Hermite Rank in Gaussian Subordination Processes

Statistical inference for time series with long-range dependence is often based on the assumption of Gaussian subordination X_t = G(Z_t). Although the Hermite rank m of G plays an essential role for statistical inference in these situations, the question of estimating m or of testing hypotheses about the Hermite rank has not been addressed in the literature. In this article, a method is introduced for testing H₀: m = 1 against H₁: m > 1. This allows for deciding whether inference based on the usual assumption of m = 1 is appropriate. Simulations and data examples illustrate the method.