Molecular properties from conformational ensembles. 1. Dipole moments of molecules with multiple internal rotations

We present a novel method for constructing the stable conformational space of small molecules with many rotatable bonds that uses our iterative stochastic elimination (ISE) algorithm, a robust stochastic search method capable of finding ensembles of best solutions for large combinatorial problems. To validate the method, we show that ISE reproduces the best conformers found in a fully exhaustive search, as well as compare computed dipole moments to experimental values, based on molecular ensembles and their Boltzmann distributions. Results were also compared to the alternative molecular dynamics and simulated annealing methods. Our results clarify that many low energy conformations may be required to reproduce molecular properties, while single low energy conformers or ensembles of low energy conformers cannot account for the experimental properties of flexible molecules. Whereas ISE well reproduces conformations that are not separated by very large energy barriers, it has not been successful in reproducing conformations of strained molecules.     

Geometric phase opens new frontiers in nonlinear frequency conversion of light

Narrow-bandgap materials possess the intriguing optical-electric properties and unique structures,which can be widely applied in the field of photonics,energy optoelectronic sensing and biomedicine,etc.Nowadays,the researches on nonlinear optical properties of narrow-bandgap materials have attracted extensive attention worldwide.In this paper,we review the progress of narrow-bandgap materials from many aspects,such as background,nonlinear optical properties,energy band structure,methods of preparation,and applications.These materials have obvious nonlinear optical characteristics and the interaction with the short pulse laser excitation shows the extremely strong nonlinear absorption characteristics,which leads to the optical limiting or saturable absorption related to Pauli blocking and excited state absorption.Especially,some of these novel narrow-bandgap materials have been utilized for the generation of ultrashort pulse that covers the range from the visible to mid-infrared wavelength regions.Hence,the study on these materials paves a new way for the advancement of optoelctronics devices.     

Emergence of Visible-Light Water Oxidation Upon Hexaniobate-Ligand Entrapment of Quantum-Confined Copper-Oxide Cores

The formation of small 1 to 3 nm organic-ligand free metal-oxide nanocrystals (NCs) is essential to utilization of their attractive size-dependent properties in electronic devices and catalysis. We now report that hexaniobate cluster-anions, [Nb₆O₁₉]⁸⁻, can arrest the growth of metal-oxide NCs and stabilize them as water-soluble complexes. This is exemplified by formation of hexaniobate-complexed 2.4-nm monoclinic-phase CuO NCs ( 1 ), whose ca. 350 Cu-atom cores feature quantum-confinement effects that impart an unprecedented ability to catalyze visible-light water oxidation with no added photosensitizers or applied potentials, and at rates exceeding those of hematite NCs. The findings point to polyoxoniobate-ligand entrapment as a potentially general method for harnessing the size-dependent properties of very small semiconductor NCs as the cores of versatile, entirely-inorganic complexes.     

Parallel search of long circular strands: modeling, analysis, and optimization

We introduce and explore a model of an ensemble of agents searching, in parallel, a long circular strand for a target site. The agents performing the search combine local-scanning (conducted by a one-dimensional motion along the strand) and random relocations on the strand. The agent-ensemble search-durations are analyzed, their limiting probability distributions are obtained in closed-form, and the optimal relocation strategies are derived. The results encompass the cases of parallel and massively parallel searches, taking place in the presence of either finite-mean or heavy-tailed relocation durations. The results are applicable to a wide spectrum of local-scans, including linear motions, Brownian motions, subdiffusive motions, fractional Brownian motions, and fractional Lévy motions.     

Transformation from an ultrashort pulse to a spatiotemporal speckle by a thin scattering surface

We have theoretically and experimentally studied the local temporal and spectral characteristics of an ultrashort pulse passing a simple thin diffusive element. We show that as one moves away from the diffuser the pulse evolves into a spatiotemporal speckle.