A new method for approximate estimates of the dispersion interaction between two molecules

A new method to evaluate the dispersion interaction between two weakly interacting closed shell molecules is presented. The method is based on a second-order sum-over-states perturbation method, where the nominator is approximated by products of one electron integrals.     

Convergent iterative schemes for time parallelization

Parallel methods are usually not applied to the time domain because of the inherit sequentialness of time evolution. But for many evolutionary problems, computer simulation can benefit substantially from time parallelization methods. In this paper, we present several such algorithms that actually exploit the sequential nature of time evolution through a predictor-corrector procedure. This sequentialness ensures convergence of a parallel predictor-corrector scheme within a fixed number of iterations. The performance of these novel algorithms, which are derived from the classical alternating Schwarz method, are illustrated through several numerical examples using the reservoir simulator Athena.

     

Spatial distribution of stabilizer-derived nitroxide radicals during thermal degradation of poly(acrylonitrile-butadiene-styrene) copolymers: a unified picture from pulsed ELDOR and ESR imaging

Double Electron-Electron Resonance (DEER) provides information on the spatial distribution of radicals on the length scale of a few nanometres, while Electron Spin Resonance Imaging (ESRI) provides information on a length scale of millimetres with a resolution of about 100 micrometres. Despite the gap between these length scales, results from the two techniques are found to complement and support each other in the characterization of the identity and distribution of nitroxide radicals derived from the Hindered Amine Stabilizer (HAS) Tinuvin 770 in poly(acrylonitrile-butadiene-styrene) (ABS) copolymers. DEER measurements demonstrate that there is no significant formation of biradicals from the bifunctional HAS, and provide the distributions of local radical concentrations. These distributions are poorly resolved for model-free analysis of the DEER data by the Tikhonov regularization; the resolution was significantly improved by utilizing information obtained by ESRI. DEER data can be fitted with only one adjustable parameter, namely the average radical concentration, if 1D and 2D spectral--spatial ESRI results on both the spatial distribution of nitroxides and their distribution between the acrylonitrile--styrene-rich (SAN) and butadiene-rich (B) microphases are considered.     

HCl and DCl: a case study of different approaches for determining photo fractionation constants

The photoabsorption cross sections of HCl and DCl are calculated using the reflection principle and time dependent wavepacket propagation methods. The absorption cross sections are compared to high precision experimental absorption cross sections from the literature and the different results given by the methods are discussed. The results of the calculations emphasize the important roles that photodissociation dynamics and the change in transition dipole moment with internuclear distance play in isotopic fractionation. The wave number dependent fractionation constants have been determined. The process fractionation constant has been calculated in the Venusian atmosphere where photo-fractionation leads to enrichment in deuterium through loss of hydrogen to space. At an altitude of 70 km the process fractionation constant was found to be epsilon(p) = -344 per thousand and epsilon(p) = -256 per thousand for the experimental and the reflection principle methods, respectively. At the top of the atmosphere the process fractionation constant was evaluated to be epsilon(p) = -32 per thousand, epsilon(p) = -20 per thousand and epsilon(p) = -40 per thousand using the experimental data, the wavepacket and the reflection principle methods, respectively. Using the Rayleigh distillation formula it is concluded that HCl at the top of the Venusian atmosphere is fractionated (enriched in D) relative to the bulk composition prior to photolysis.     

Nanosecond-Flash 15N Photo-CIDNP MAS NMR on Reaction Centers of Rhodobacter sphaeroides R26

Photochemically induced dynamic nuclear polarization (photo-CIDNP) is observed with time-resolved ¹⁵N magic-angle spinning (MAS) nuclear magnetic resonance (NMR) in uniformly ¹⁵N-labeled reaction centers (RCs) of the purple bacterium Rhodobacter (Rb.) sphaeroides R26 under illumination with nanosecond laser flashes. The ¹⁵N NMR signals enhanced by the solid-state photo-CIDNP effect are related to electron spin densities in the primary radical pair and allow for reconstruction of the electronic structure at atomic scale. New assignments for the photochemically active nitrogens are proposed based on simulations of the intensities. The ratio of electron spin densities between cofactors P _L and P _M is observed to be about 4:1. The origin of the high asymmetry is discussed.     

Normalized LMS digital filter for chromatic dispersion equalization in 112-Gbit/s PDM-QPSK coherent optical transmission system

High bit rates optical communication systems pose the challenge of their tolerance to linear and non-linear fiber impairments. Coherent optical receivers using digital signal processing techniques can mitigate the fiber impairments in the optical transmission system, including the chromatic dispersion equalization with digital filters. In this paper, an adaptive finite impulse response filter employing normalized least mean square algorithm is developed for compensating the chromatic dispersion in a 112-Gbit/s polarization division multiplexed quadrature phase shift keying coherent communication system, which is established in the VPI simulation platform. The principle of the adaptive normalized least mean square algorithm for signal equalization is analyzed theoretically, and at the meanwhile, the taps number and the tap weights in the adaptive finite impulse response filter for compensating a certain fiber chromatic dispersion are also investigated by numerical simulation. The chromatic dispersion compensation performance of the adaptive filter is analyzed by evaluating the behavior of the bit-error-rate versus the optical signal-to-noise ratio, and the compensation results are also compared with other present digital filters.