Computational protocols for prediction of solute NMR relative chemical shifts. a case study of L-tryptophan in aqueous solution

In this study, we have applied two different spanning protocols for obtaining the molecular conformations of L-tryptophan in aqueous solution, namely a molecular dynamics simulation and a molecular mechanics conformational search with subsequent geometry re-optimization of the stable conformers using a quantum mechanically based method. These spanning protocols represent standard ways of obtaining a set of conformations on which NMR calculations may be performed. The results stemming from the solute-solvent configurations extracted from the MD simulation at 300 K are found to be inferior to the results stemming from the conformations extracted from the MM conformational search in terms of replicating an experimental reference as well as in achieving the correct sequence of the NMR relative chemical shifts of L-tryptophan in aqueous solution. We find this to be due to missing conformations visited during the molecular dynamics run as well as inaccuracies in geometrical parameters generated from the classical molecular dynamics simulations.     

Retracing the residual curve of a Lyapunov equation solver

Let A∈ℝ ^n×n and let B∈ℝ ^n×p and consider the Lyapunov matrix equation AX+XA ^T +BB ^T =0. If A+A ^T <0, then the extended Krylov subspace method (EKSM) can be used to compute a sequence of low rank approximations of X. In this paper we show how to construct a symmetric negative definite matrix A and a column vector B, for which the EKSM generates a predetermined residual curve.     

Lidar calibration experiments

A series of atmospheric aerosol diffusion experiments combined with lidar detection was conducted to evaluate and calibrate an existing retrieval algorithm for aerosol backscatter lidar systems. The calibration experiments made use of two (almost) identical mini-lidar systems for aerosol cloud detection to test the reproducibility and uncertainty of lidars. Lidar data were obtained from both single-ended and double-ended lidar configurations. A backstop was introduced in one of the experiments and a new method was developed where information obtained from the backstop can be used in the inversion algorithm. Independent in-situ aerosol plume concentrations were obtained from a simultaneous tracer gas experiment with SF, and comparisons with the two lidars were made. The study shows that the reproducibility of the lidars is within 15%, including measurements from both sides of a plume. The correspondence with in-situ measurements is excellent. Finally, the new backstop method is able to reveal information which can close the lidar equation by obtaining the relation between backscatter and extinction in an aerosol cloud. Received: 21 December 1995 / Revised version: 25 July 1996     

Field descriptions for a steady,developing tube flow of vanishing Reynolds number

Numerical solutions for the stream function, vorticity, velocity, and pressure fields are presented for the case of a steady, laminar, isothermal, Newtonian flow developing from an initial slug flow in a circular cylinder of infinite length at zero Reynolds number.     

Thermal expansivity in superionic RbAg4I5

We have measured the length of a RbAg₄I₅ crystal in the temperature range between 130 K and 300 K using a fused silica LVDT dilatometer system. The expansivity is a smooth, nearly linear function of temperature. There is no anomaly such as a kink, discontinuity, or critical behavior at T_c = 209 K where the superionic β to superionic α phase transition occurs.     

An interactive system for the loading of cargo aircraft

The paper describes an interactice, computer based procedure for solving the variant of the vehicle loading problem encountered when loading containers and pallets into an aircraft. The procedure is heuristic and practical oriented; it is presently being implemented by Scandinavian Airlines.     

Quantum nature of the sign preference in ion-induced nucleation

Observed first in Wilson's pioneering experiments in the cloud chamber, the sign preference has remained a mystery for more than a century. We investigate the sign preference using a quantum approach and show that this puzzling phenomenon is essentially quantum in nature. It is shown that the effect of the chemical identity of the core ion is controlled by the electronic structure of the core ion through the influence on the intermolecular bonding energies during the initial steps of cluster formation. Our results demonstrate the superiority of the quantum approach and indicate fundamental problems of conventional ion-induced nucleation theories, in which the electronic structure of the core ion is either ignored or not treated rigorously.     

Simulation of the inherent turbulence and wake interaction inside an infinitely long row of wind turbines

The turbulence in the interior of a wind farm is simulated using large eddy simulation and the actuator line technique implemented in the Navier–Stokes equations. The simulations are carried out for an infinitely long row of turbines simulated by applying cyclic boundary conditions at the inlet and outlet. The simulations investigate the turbulence inherent to the wind turbines as no ambient turbulence or shear is added to this idealised case. The simulated data give insight into the performance of the wind turbines operating in the wake of others as well as details on key turbulent quantities. One of the key features of wakes behind wind turbines is the dynamic wake meandering, which is shown to be related to the wind turbine spacing and the vortex shedding from the turbine as a bluff body. The flow is analysed and reconstructed by applying proper orthogonal decomposition.     

Luminescence Spectroscopy of Rhodamine Homodimer Dications in Vacuo Reveals Strong Dye-Dye Interactions

Being alone or together makes a difference for the photophysics of dyes but for ionic dyes it is difficult to quantify the interactions due to solvent screening and nearby counter ions. Gas-phase luminescence experiments are desirable and now possible based on recent developments in mass spectrometry. Here we present results on tailor-made rhodamine homodimers where two dye cations are separated by methylene linkers, (CH₂)_n. In solution the fluorescence is almost identical to that from the monomer whereas the emission from bare cation dimers redshifts with decreasing n. In the absence of screening, the electric field from the charge on one dye is strong enough to polarize the other dye, both in the ground state and in the excited state. An electrostatic model based on symmetric dye responses (equal induced-dipole moments in ground state) captures the underlying physics and demonstrates interaction even at large distances. Our results have possible implications for gas-phase Förster Resonance Energy Transfer.     

An optimal semiclassical bound on commutators of spectral projections with position and momentum operators

Letters in Mathematical Physics - We prove an optimal semiclassical bound on the trace norm of the following commutators $$[{\varvec{1}}_{(-\infty ,0]}(H_\hbar ),x]$$ , $$[{\varvec{1}}_{(-\infty...