非平衡溶剂化新理论在有机染料电子光谱中的应用

总结了非平衡溶剂化新理论和在量子化学软件Q-Chem中基于含时密度泛函理论(TD-DFT)实现溶剂效应下计算电子吸收和发射光谱的数值解方法.采用该方法计算了染料敏化太阳能电池(DSSCs)中三苯胺型有机染料■在真空和乙腈溶剂中的电子结构与光谱性质,研究发现,π共轭桥上碳碳双键的个数和溶剂效应会促进光电转换.     

Radiation in a hypersonic shock layer generated around a projectile

Radiation emitted from the shock layer generated around a hypersonic flight model is experimentally investigated by using a ballistic range (two-stage light-gas gun). A polyethylene projectile of 1.2 cm in diameter is launched in this facility at the velocity of 5 km/sec (M=15), and the emission from the induced shock layer around the projectile is observed with a spectroscope. As a result, molecular band-spectra from NO and N₂ are detected along with those from carboncontaining molecules. Total emission power is measured with a diode-type powermeter. In addition, dimension effect of the flight model is theoretically and numerically examined, and a scaling law on thermochemical structure of the shock layer is developed. It shows that the thickness of thermal boundary-layer formed on the model surface does not follow the conventional scaling law based on the reaction distance and on the energy relaxation distance. Finally, the radiative field around the projectile is numerically computed, and the total power emitted from the shock layer is estimated. From the comparison between computed and measured results, the validity of the calculation model is discussed.     

Energy elastic effects and the concept of temperature in flowing polymeric liquids

The incorporation of energy elastic effects in the modeling of flowing polymeric liquids is discussed. Since conformational energetic effects are determined by structural features much smaller than the end-to-end vector of the polymer chains, commonly employed single conformation tensor models are insufficient to describe energy elastic effects. The need for a local structural variable is substantiated by studying a microscopic toy model with energetic effects in the setting of a generalized canonical ensemble. In order to examine the dynamics of flowing polymeric liquids with energy elastic effects, a thermodynamically admissible set of evolution equations is presented that accounts for the evolution of the microstructure in terms of a slow tensor, as well as a fast, local scalar variable. It is demonstrated that the temperature used in the definition of the heat flux is directly related to the Lagrange multiplier of the microscopic energy in the generalized canonical partition function. The temperature equation is discussed with respect to, first, the dependence of the heat capacity on the polymer conformation and, second, the possibility to measure experimentally the effects of the conformational energy.

Electrical switching effect in a photochromic molecule between two graphene electrodes

We propose a single-molecule electrical switches consisting of a photochromic dimethyldihydropyrene/cyclophanediene molecule sandwiched between two graphene electrodes and investigate the electronic transport by using density-functional theory and nonequilibrium Green's function methods. The “open” and “closed” isomers of the photochromic molecule are shown to have electrical switching behavior and negative differential resistance effect. Moreover, it is also found that the switching ratio between two different conductive states depends on the ambient temperature, and the device behaves as a stable electrical switch around room temperature, which is in agreement with a recent experimental study of another photochromic molecule diarylethene reported by Jia et al. (2016) [17].     

Unifying treatment of nonequilibrium and unstable dynamics of cold bosonic atom system with time-dependent order parameter in Thermo Field Dynamics

The coupled equations which describe the temporal evolution of the Bose–Einstein condensed system are derived in the framework of nonequilibrium Thermo Field Dynamics. The key element is that they are not the naive assemblages of assumed equations, but are the self-consistent ones derived by appropriate renormalization conditions. While the order parameter is time-dependent, an explicit quasiparticle picture is constructed by a time-dependent expansion. Our formulation is valid even for the system with a unstable condensate, and describes the condensate decay caused by the Landau instability as well as by the dynamical one.     

Transition state theory: A generalization to nonequilibrium systems with power-law distributions

Transition state theory (TST) is generalized to nonequilibrium systems with power-law distributions. The stochastic dynamics that gives rise to the power-law distributions for the reaction coordinate and momentum is modeled by Langevin equations and corresponding Fokker-Planck equations. It is considered that a system far away from equilibrium does not have to relax to a thermal equilibrium state with Boltzmann-Gibbs distribution, but asymptotically approaches a nonequilibrium stationary state with a power-law distribution. Thus, we obtain a possible generalization of TST rates to nonequilibrium systems with power-law distributions. Furthermore, we derive the generalized TST rate constants for one-dimensional and n-dimensional Hamiltonian systems away from equilibrium, and obtain a generalized Arrhenius rate for systems with power-law distributions.     

Finite-size effects in the self-organized critical forest-fire model

We study finite-size effects in the self-organized critical forest-fire model by numerically evaluating the tree density and the fire size distribution. The results show that this model does not display the finite-size scaling seen in conventional critical systems. Rather, the system is composed of relatively homogeneous patches of different tree densities, leading to two qualitatively different types of fires: those that span an entire patch and those that do not. As the system size becomes smaller, the system contains less patches, and finally becomes homogeneous, with large density fluctuations in time. Received 24 April 1999 and Received in final form 26 October 1999     

Reaction-diffusion system with self-organized critical behavior

We describe the construction of a conserved reaction-diffusion system that exhibits self-organized critical (avalanche-like) behavior under the action of a slow addition of particles. The model provides an illustration of the general mechanism to generate self-organized criticality in conserving systems. Extensive simulations in d = 2 and 3 reveal critical exponents compatible with the universality class of the stochastic Manna sandpile model. Received 16 November 2000