Spectral Diffusion of Single Molecules in a Hierarchical Energy Landscape

Spectral diffusion as a result of both the transitions between different molecular conformers and the ′′molecular softness′′ of quasi‐free perylene diimides on a SiO₂ surface is investigated by means of single‐molecule spectroscopy, which reveals the time dependence of both the fluorescence spectra and the three‐dimensional orientation. Spectral wavelengths of all single emitters cover a wide energy range of about 0.27 eV, which is due to different types of conformers with large differences in optical transition energy. Time‐dependent spectral trajectories of single emitters within this wavelength manifold are evaluated with a model transcribed from the analysis of spatial diffusion. Spectral diffusion processes are closely correlated with fluorescence emission and excitation power. The overall analysis of spectral diffusion reveals, similar to proteins, a hierarchy of energy barriers in a broad energy landscape.     

一种基于数独的新试验设计

通过研究数独方的构成与设计,建立了一种基于数独的新试验设计,给出了这种设计的数学模型与统计分析。该设计能安排单因素的n个水平,并能在行、列、块3个方向控制变异性。     

Towards a unified view of fluids

It has traditionally been believed that, unlike normal fluids whose structural properties are determined primarily by the intermolecular short-range repulsive interactions, the properties of polar and associating fluids are strongly affected by the long-range Coulombic interactions. In the course of investigations to determine the primary driving forces governing the behaviour of various (non-simple) fluids, and hence to gain a deeper understanding of the molecular mechanisms leading to the development of theoretically based simple models and theory, extensive and systematic computer simulations have been performed on typical quadrupolar (carbon dioxide), dipolar (acetone and acetonitrile), and associating (hydrogen fluoride, methanol, and water) fluids using the available realistic effective pair potentials and their variants involving forces of different ranges. In addition to the main structural characteristics (one- and two-dimensional site–site correlation functions, local g factors, and radial slices through the full pair correlation function), the dielectric constants and the thermodynamic properties (internal energy and pressure) of both the homogeneous liquid and supercritical fluid phases, and vapor–liquid equilibria have also been considered. Furthermore, in the case of water, the diffusion coefficient and viscosity have also been considered along with water at the interface. All the obtained results lead to the unambiguous conclusion that the structure, defined in terms of the complete set of site–site correlation functions, for both polar and associating pure fluids is governed by the same molecular mechanism as for normal fluids, i.e. by the short-range interactions (which, however, may be both repulsive and attractive), whereas the long-range part of the electrostatic forces, regardless of their strength, plays only a marginal role and may be treated as a perturbation only. The consequences of these findings for theory and applications are also discussed.