Full dimensional (15-dimensional) quantum-dynamical simulation of the protonated water dimer. II. Infrared spectrum and vibrational dynamics

The infrared absorption spectrum of the protonated water dimer (H5O2+) is simulated in full dimensionality (15 dimensional) in the spectral range of 0-4000 cm(-1). The calculations are performed using the multiconfiguration time-dependent Hartree (MCTDH) method for propagation of wavepackets. All the fundamentals and several overtones of the vibrational motion are computed. The spectrum of H5O2+ is shaped to a large extent by couplings of the proton-transfer motion to large amplitude fluxional motions of the water molecules, water bending and water-water stretch motions. These couplings are identified and discussed, and the corresponding spectral lines are assigned. The large couplings featured by H5O2+ do not hinder, however, to describe the coupled vibrational motion by well defined simple types of vibration (stretching, bending; etc.) based on well defined modes of vibration, in terms of which the spectral lines are assigned. Comparison of our results to recent experiments and calculations on the system is given. The reported MCTDH IR spectrum is in very good agreement to the recently measured spectrum by Hammer et al. [J. Chem. Phys. 122, 244301 (2005)].     

Acido-triggered nonlinear optical switches: benzazolo-oxazolidines

This work is the continuation of our previous experimental and theoretical studies aiming at designing efficient nonlinear optical (NLO) switches derived from the benzazolo-oxazolidine core. Here, we report the synthesis and the characterization of the linear and nonlinear optical properties of benzothiazolo[2,3-b]oxazolidine acidochromes by means of hyper-Rayleigh scattering as well as quantum chemical calculations. It is shown that these new derivatives incorporating a benzothiazole subunit exhibit very high static first hyperpolarizability values in their acido-generated form. On the basis of previously reported NLO responses of indolino- and benzimidazolo-oxazolidines, structure-properties relationships within the benzazolo-oxazolidine series are proposed.     

syn additions to 4alpha-epoxypyranosides: synthesis of L-idopyranosides

The syn-selective addition of organozinc compounds to 4alpha-epoxypyranosides (4alpha-EPs), generated from methyl beta-D-glucoside or aminoglucoside, provides an efficient route to pyranosides with alpha-L-ido configurations, including L-iduronic acid, neosamine B, and higher monosaccharide derivatives.     

Assessment of conformational ensemble sizes necessary for specific resolutions of coverage of conformational space

The size of conformational ensembles required for regular coverage of the conformational space of druglike molecules was examined. Using the conformer generation program Omega, the number of regularly distributed conformers (NRC) of flexible compounds was determined as a function of the root-mean-square deviation (RMSD) resolution of coverage. A regression equation was developed predicting the NRC of a molecule as a function of RMSD. The model yielded R(2) of 0.91 for both training and test sets, which consisted of 3414 and 3352 compounds, respectively. Utilizing 14 504 ligands from the Protein Data Bank with experimentally determined 3-D conformations, the regression equation was applied to the estimation of the NRC and the success rate of reproduction of experimental conformations from a theoretical conformation ensemble as a function of RMSD and flexibility was explored.     

A novel, facile route to beta-fluoroamines by hydrofluorination using superacid HF-SbF(5)

A range of unsaturated amines and sulfonamides were converted to beta-fluoro nitrogen analogues after hydrofluorination in superacid HF-SbF(5), based on the formation of highly reactive electrophilic intermediates.     

A new symmetric interior penalty discontinuous Galerkin formulation for the Serre–Green–Naghdi equations

In this work, we investigate the construction of a new discontinuous Galerkin discrete formulation to approximate the solution of Serre–Green–Naghdi (SGN) equations in the one-dimensional horizontal framework. Such equations describe the time evolution of shallow water free surface flows in the fully nonlinear and weakly dispersive asymptotic approximation regime. A new non-conforming discrete formulation belonging to the family of symmetric interior penalty discontinuous Galerkin methods is introduced to accurately approximate the solutions of the second order elliptic operator occurring in the SGN equations. We show that the corresponding discrete bilinear form enjoys some consistency and coercivity properties, thus ensuring that the corresponding discrete problem is well-posed. The resulting global discrete formulation is then validated through an extended set of benchmarks, including convergence studies and comparisons with data taken from experiments.     

Localized excitations in arrays of synchronized laser oscillators

We investigate the spatiotemporal dynamics of a large array of laser oscillators. The oscillators are locally coupled and their natural frequencies are randomly detuned. We show that synchronization of the array elements results in localized excitations wandering along well-defined trajectories.     

High spectral purity and tunable operation of a continuous singly resonant optical parametric oscillator emitting in the red

Continuous-wave oscillation of a singly resonant optical parametric oscillator operating from 619 to 640 nm has been obtained. Parametric gain is created in a MgO-doped periodically poled stoichiometric lithium tantalate crystal pumped at 532 nm. 100 mW of single-frequency red light have been generated. The signal frequency is tunable, and its frequency stabilization on an external reference has been achieved.     

Shot-noise-limited operation of a monomode high-cavity-finesse semiconductor laser for microwave photonics applications

Shot-noise-limited laser operation over a wide spectral bandwidth is demonstrated by using a semiconductor active medium inserted into a high-Q external cavity. This approach ensures, with a compact design, a sufficiently long photon lifetime to reach the oscillation-relaxation-free class A regime. The laser relative intensity noise is limited to the shot-noise relative floor, -156 dB/Hz for a 1 mA detected photocurrent, over the 100 MHz to 18 GHz bandwidth. The optimization of the laser cavity is discussed, and convenient shot-noise-limited operation is shown to be a trade-off between the cavity length and laser mode filtering.