Direct Observation of Thermal Equilibrium of Excited Triplet States of 9,10-Phenanthrenequinone. A Time-Resolved Resonance Raman Study

The photochemistry of aromatic ketones plays a key role in various physicochemical and biological processes, and solvent polarity can be used to tune their triplet state properties. Therefore, a comprehensive analysis of the conformational structure and the solvent polarity induced energy level reordering of the two lowest triplet states of 9,10-phenanthrenequinone (PQ) was carried out using nanosecond-time-resolved absorption (ns-TRA), time-resolved resonance Raman (TR3) spectroscopy, and time dependent-density functional theory (TD-DFT) studies. The ns-TRA of PQ in acetonitrile displays two bands in the visible range, and these two bands decay with similar lifetime at least at longer time scales (mu s). Interestingly, TR3 spectra of these two bands indicate that the kinetics are different at shorter time scales (ns), while at longer time scales they followed the kinetics of ns-TRA spectra. Therefore, we report a real-time observation of the thermal equilibrium between the two lowest triplet excited states of PQ assigned to n pi* and pi pi* of which the pi pi* triplet state is formed first through intersystem crossing. Despite the fact that these two states are energetically close and have a similar conformational structure supported by TD-DFT studies, the slow internal conversion (similar to 2 ns) between the T-2(1(3)n pi*) and T-1(1(3)pi pi*) triplet states indicates a barrier. Insights from the singlet excited states of PQ in protic solvents J. Chem. Phys. 2015, 142, 24305] suggest that the lowest n pi* and pi pi* triplet states should undergo hydrogen bond weakening and strengthening, respectively, relative to the ground state, and these mechanisms are substantiated by TD-DFT calculations. We also hypothesize that the different hydrogen bonding mechanisms exhibited by the two lowest singlet and triplet excited states of PQ could influence its ISC mechanism.

Supersymmetry: Boundary conditions and edge states

When spatial boundaries are inserted, supersymmetry (SUSY) can be broken. We have shown that in an N = 2 supersymmetric theory, all local boundary conditions allowed by self-adjointness of the Hamiltonian break N = 2 SUSY, while only a few of these boundary conditions preserve N = 1 SUSY. We have also shown that for a subset of the boundary conditions compatible with N = 1 SUSY, there exist fermionic ground states which are localized near the boundary. We also show that only very few nonlocal boundary conditions like periodic boundary conditions preserve full N = 2 supersymmetry, but none of them exhibits edge states.

Edge states, spin transport, and impurity-induced local density of states in spin-orbit coupled graphene

We study graphene, which has both spin-orbit coupling (SOC), taken to be of the Kane-Mele form, and a Zeeman field induced due to proximity to a ferromagnetic material. We show that a zigzag interface of graphene having SOC with its pristine counterpart hosts robust chiral edge modes in spite of the gapless nature of the pristine graphene; such modes do not occur for armchair interfaces. Next we study the change in the local density of states (LDOS) due to the presence of an impurity in graphene with SOC and Zeeman field, and demonstrate that the Fourier transform of the LDOS close to the Dirac points can act as a measure of the strength of the spin-orbit coupling; in addition, for a specific distribution of impurity atoms, the LDOS is controlled by a destructive interference effect of graphene electrons which is a direct consequence of their Dirac nature. Finally, we study transport across junctions, which separates spin-orbit coupled graphene with Kane-Mele and Rashba terms from pristine graphene both in the presence and absence of a Zeeman field. We demonstrate that such junctions are generally spin active, namely, they can rotate the spin so that an incident electron that is spin polarized along some direction has a finite probability of being transmitted with the opposite spin. This leads to a finite, electrically controllable, spin current in such graphene junctions. We discuss possible experiments that can probe our theoretical predictions.

Asymptotic behavior and interpretation of virtual states: The effects of confinement and of basis sets

A real-space high order finite difference method is used to analyze the effect of spherical domain size on the Hartree-Fock (and density functional theory) virtual eigenstates. We show the domain size dependence of both positive and negative virtual eigenvalues of the Hartree-Fock equations for small molecules. We demonstrate that positive states behave like a particle in spherical well and show how they approach zero. For the negative eigenstates, we show that large domains are needed to get the correct eigenvalues. We compare our results to those of Gaussian basis sets and draw some conclusions for real-space, basis-sets, and plane-waves calculations. (C) 2016 AIP Publishing LLC.

Strength of Offshore Pipelines in Different Operation States and Analyzing Software

在近海管线的铺设、安装、使用过程中有多种作业状态：在位、悬跨、挖沟、提吊、铺管等。各种状态下管线的受力特点不同,加上管线结构、海况和海底土壤等因素又都很复杂,所以近海管线的强度分析难度大、内容多。分别采用解析方法、数值方法（有限元法、打靶法）和二者结合来解决理论上的（如几何非线性、动边界等）、实用性方面的难点。在理论分析的基础上,编制了符合产业部门工程师使用要求的近海管线强度分析软件。介绍了该软件进行力学分析时采用的理论以及软件界面。

Population of nonnative states of lysozyme variants drives amyloid fibril formation.

The propensity of protein molecules to self-assemble into highly ordered, fibrillar aggregates lies at the heart of understanding many disorders ranging from Alzheimer's disease to systemic lysozyme amyloidosis. In this paper we use highly accurate kinetic measurements of amyloid fibril growth in combination with spectroscopic tools to quantify the effect of modifications in solution conditions and in the amino acid sequence of human lysozyme on its propensity to form amyloid fibrils under acidic conditions. We elucidate and quantify the correlation between the rate of amyloid growth and the population of nonnative states, and we show that changes in amyloidogenicity are almost entirely due to alterations in the stability of the native state, while other regions of the global free-energy surface remain largely unmodified. These results provide insight into the complex dynamics of a macromolecule on a multidimensional energy landscape and point the way for a better understanding of amyloid diseases.

Limiting States Of Internal Wave Rays

Existing models of baroclinic tides are based upon the "traditional approximation'', i. e., neglect of the horizontal component of the Earth's rotation, leading to a well- known conclusion that no freely propagating internal waves can exist beyond the critical latitude and the wave rays are symmetric to the vertical. However, recent studies have contended that the situation may change if both the vertical and horizontal components of the Earth's rotation are taken into account. With the full account of the Coriolis force, characteristics of the internal wavefield generated by tidal flow over uneven topography are investigated. It is found that "nontraditional effects'' profoundly change not only the dynamics of internal waves but also the rate at which the barotropic tidal energy is fed into the internal wavefield. Discarding the traditional approximation, internal waves are proved to be able to generate poleward of the critical latitude, rays of which are no longer symmetric and the limiting values of ray angles become greater or less than 90 degrees, depending on the local latitude and the direction of ray. More importantly, in contrast to the predictions of models based upon the traditional approximation, a substantial conversion occurs in the situations when stratification is so weak that the buoyancy frequency is below the tidal one.

Fishery resources of the United States of America

The term “fishery resources” is used in this book with a broad application. It includes the populations of the fishes and other organisms useful to men, the environment that makes life possible for them, the industry that exploits and utilizes them, and our knowledge about them by which we can conserve their productivity. This book aims to survey the present status of all these aspects of those fishery resources that are used or are available for use by United States anglers and commercial fishermen. It is planned primarily for the Congress, at its request, with the idea of giving to busy people, in condensed fashion, a perspective on its subject. (pdf contains 142 pages)