Dynamical Bifurcation in Gas‐Phase XH− + CH3Y SN2 Reactions: The Role of Energy Flow and Redistribution in Avoiding the Minimum Energy Path

The gas‐phase reactions of XH^? (X=O, S) + CH₃Y (Y=F, Cl, Br) span nearly the whole range of S_N2 pathways, and show an intrinsic reaction coordinate (IRC) (minimum energy path) with a deep well owing to the CH₃XH???Y^? (or CH₃S^????HF) hydrogen‐bonded postreaction complex. MP2 quasiclassical‐type direct dynamics starting at the [HX???CH₃???Y]^? transition‐state (TS) structure reveal distinct mechanistic behaviors. Trajectories that yield the separated CH₃XH+Y^? (or CH₃S^?+HF) products directly are non‐IRC, whereas those that sample the CH₃XH???Y^? (or CH₃S^????HF) complex are IRC. The IRCIRC/non‐IRC ratios of 90:10, 40:60, 25:75, 2:98, 0:100, and 0:100 are obtained for (X, Y)=(S, F), (O, F), (S, Cl), (S, Br), (O, Cl), and (O, Br), respectively. The properties of the energy profiles after the TS cannot provide a rationalization of these results. Analysis of the energy flow in dynamics shows that the trajectories cross a dynamical bifurcation, and that the inability to follow the minimum energy path arises from long vibration periods of the X?C???Y bending mode. The partition of the available energy to the products into vibrational, rotational, and translational energies reveals that if the vibrational contribution is more than 80 %, non‐IRC behavior dominates, unless the relative fraction of the rotational and translational components is similar, in which case a richer dynamical mechanism is shown, with an IRC/non‐IRC ratio that correlates to this relative fraction.     

On the signal degradation induced by the interpolation and the sampling rate reduction in aeroacoustics hybrid methods

Taking place within more extensive work that focuses on hybrid methods in aeroacoustics, the present study is devoted to the data transfer operations that are to be performed between two stages of a hybrid calculation. More precisely, the article focuses on two typical operations that usually accompany such data transfer, which are (i) the sampling rate reduction and (ii) the interpolation of the unsteady perturbations to be transmitted from one stage to the other. First part of the paper analyzes the two main issues of such operations, which are the spuriousing and the aliasing phenomena. For doing so, the usual notions of the interpolation theory are revisited before they are synthesized within an original approach. The here proposed formalism allows to understand better both the spuriousing and the aliasing phenomena, as well as to accurately predict the impact of the latter on the data to be transmitted in terms of signal degradation. Second part of the paper provides an illustration and a validation of these theoretical developments via a direct application to a typical aerodynamic noise problem (aeroacoustic emission by a 2D cylinder cross flow). There, it is further shown how the here proposed formalism can help in improving aeroacoustics hybrid calculations by predicting (and thus possibly minimizing) the bias to be induced on the acoustic extrapolation stage because of the aliasing and/or spuriousing effects inherited from the sampling rate reduction and/or interpolation of CFD data—which is likely to occur in any hybrid scenario. Copyright © 2012 John Wiley & Sons, Ltd.     

Coherent transfer by adiabatic passage in two-dimensional lattices

Coherent tunneling by adiabatic passage (CTAP) is a well-established technique for robust spatial transport of quantum particles in linear chains. Here we introduce two exactly-solvable models where the CTAP protocol can be extended to two-dimensional lattice geometries. Such bi-dimensional lattice models are synthesized from time-dependent second-quantization Hamiltonians, in which the bosonic field operators evolve adiabatically like in an ordinary three-level CTAP scheme thus ensuring adiabatic passage in Fock space.     

Hydroxyl Radical Generation and DNA Nuclease Activity: A Mechanistic Study Based on a Surface‐Immobilized Copper Thioether Clip‐Phen Derivative

Coordination compounds of copper have been invoked as major actors in processes involving the reduction of molecular oxygen, mostly with the generation of radical species the assignment for which has, so far, not been fully addressed. In the present work, we have carried out studies in solution and on surfaces to gain insights into the nature of the radical oxygen species (ROS) generated by a copper(II) coordination compound containing a thioether clip‐phen derivative, 1,3‐bis(1,10‐phenanthrolin‐2‐yloxy)‐N‐(4‐(methylthio)benzylidene)propan‐2‐amine (2CP‐Bz‐SMe), enabling its adsorption/immobilization to gold surfaces. Whereas surface plasmon resonance (SPR) and electrochemistry of the adsorbed complex indicated the formation of a dimeric Cu^I intermediate containing molecular oxygen as a bridging ligand, scanning electrochemical microscopy (SECM) and nuclease assays pointed to the generation of a ROS species. Electron paramagnetic resonance (EPR) data reinforced such conclusions, indicating that radical production was dependent on the amount of oxygen and H₂O₂, thus pointing to a mechanism involving a Fenton‐like reaction that results in the production of OH^..     

Exactly solvable chain of interacting electrons with correlated hopping and pairing

A generalization of the Mattis-Nam model Mattis and Nam (1972) [7], which takes into account a correlated hopping and pairing of electrons, is proposed, its exact solution is obtained. In the framework of the model the stability of the zero energy Majorana fermions localized at the boundaries is studied in the chain in which electrons interact through both the on-site Hubbard interaction and the correlated hopping and pairing. The ground-state phase diagram of the model is calculated, the region of existence of topological states is determined. It is shown that low-energy excitations destroy bonds between electrons in the chain, leading to an insulator state.     

二维胶体玻璃中玻色峰与结构无序度的关联

本文从实验上研究了胶体玻璃在相同面密度下随着体系结构无序程度的增加, 振动态密度和玻色峰的变化规律. 通过调制两种不同粒径的温敏性水凝胶的数量比来改变体系的无序程度. 通过分析无序体系的声子模式得到体系的振动特性. 研究发现, 随着无序度的增加, 态密度在低频区域增强、玻色峰增高、玻色峰的峰值向低频区域移动. 不同无序程度的样品引起玻色峰的低频声子模式都表现出准局域的特点, 且低频准局域声子模式与样品中无序结构存在关联.     

Heavy-Atom Tunneling in Semibullvalenes: How Driving Force,Substituents, and Environment Influence the Tunneling Rates

The Cope rearrangement of selectively deuterated isotopomers of 1,5-dimethylsemibullvalene 2 a and 3,7-dicyano-1,5-dimethylsemibullvalene 2 b were studied in cryogenic matrices. In both semibullvalenes the Cope rearrangement is governed by heavy-atom tunneling. The driving force for the rearrangements is the small difference in the zero-point vibrational energies of the isotopomers. To evaluate the effect of the driving force on the tunneling probability in 2 a and 2 b , two different pairs of isotopomers were studied for each of the semibullvalenes. The reaction rates for the rearrangement of 2 b in cryogenic matrices were found to be smaller than the ones of 2 a under similar conditions, whereas differences in the driving force do not influence the rates. Small curvature tunneling (SCT) calculations suggest that the reduced tunneling rate of 2 b compared to that of 2 a results from a change in the shape of the potential energy barrier. The tunneling probability of the semibullvalenes strongly depends on the matrix environment; however, for 2 a in a qualitatively different way than for 2 b .     

政府奖励对报废汽车回收模式选择的作用机制研究——基于企业社会责任视角

随着我国报废汽车数量的增多,由其造成的交通隐患、环境污染和资源浪费已成为重要社会问题,而如何设计合理可行的回收模式成为解决问题的关键。以制造商主导为前提,提出了基于企业社会责任的报废汽车回收模型,构建了制造商回收、销售商回收和第三方回收模式下的回收流程和数学模型,通过实例对考虑和不考虑企业社会责任两种情况下的回收模型进行了分析,探讨了不同政府奖励下报废汽车回收模式的策略选择。通过研究发现:(1)不论是否考虑企业社会责任,随着政府奖励的增加,制造商最终都会选择由自己进行回收;(2)当考虑企业社会责任时,政府奖励和决策者经济责任偏好都会导致决策的改变,随着政府奖励和赋予经济责任权重的同步增加,制造商的决策由第三方企业回收模式或销售商回收模式变成了制造商回收模式,表明政府奖励和企业社会责任对报废汽车回收模式选择具有显著影响。