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].     

Nonequilibrium potential for arbitrary-connected networks of FitzHugh-Nagumo elements

We study an array of N units with FitzHugh-Nagumo dynamics linearly coupled. The system is submitted to a subthreshold harmonic signal and independent Gaussian white noises with a common intensity η. In the limit of adiabatic driving, we analytically calculate the system’s nonequilibrium potential for arbitrary linear coupling. We illustrate its applicability by investigating noise-induced effects in an excitable regular network with extended antiphase coupling. In particular, the levels of noise for short-wavelength phase-instability, network’s synchronization and depinning of “defects” (groups of contiguous inhibited neurons on an antiphase background) are theoretically predicted and numerically confirmed. The origin of these collective effects and the dependence with parameters of the most probable length of defects are explained in terms of the system’s nonequilibrium potential.     

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.     

Solvent Reorganization Energy and Electronic Coupling for Intramolecular Electron Transfer in Biphenyl-Acceptor Anion Radicals

基于非平衡溶剂化理论和连续介质模型修改了GAMESS中的相关程序，实现了电子转移溶剂重组能的数值计算. 采用修改后的程序计算得到了联苯-雄甾烷-萘和联苯-雄甾烷-菲这两个体系电子转移的溶剂重组能约为60 kJ/mol. 这个结果与实验拟合值符合的很好. 利用线性反应坐标与Koopmans定理计算了电子转移耦合矩阵元，结果与实验拟合值有可比性.     

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     

Multicomponent transport algorithms for partially ionized mixtures

We investigate iterative methods for solving linear systems arising from the kinetic theory of gases and providing multicomponent transport coefficients of partially ionized plasmas. We consider the situations of weak and strong magnetic fields as well as electron temperature nonequilibrium and the linear systems are investigated in their natural constrained singular symmetric form. Stationary iterative techniques are considered with new more singular formulations of the transport linear systems as well as orthogonal residuals algorithms. The new formulations are derived by considering generalized inverses with nullspaces of increasing dimension. Numerical tests are performed with high temperature air and iterative techniques lead to fast and accurate evaluation of the transport coefficients for all ionization levels and magnetic field intensities.