Geometrical Models of the Phase Space Structures Governing Reaction Dynamics

Hamiltonian dynamical systems possessing equilibria of ${saddle} \times {centre} \times...\times {centre}$ stability type display \emph{reaction-type dynamics} for energies close to the energy of such equilibria; entrance and exit from certain regions of the phase space is only possible via narrow \emph{bottlenecks} created by the influence of the equilibrium points. In this paper we provide a thorough pedagogical description of the phase space structures that are responsible for controlling transport in these problems. Of central importance is the existence of a \emph{Normally Hyperbolic Invariant Manifold (NHIM)}, whose \emph{stable and unstable manifolds} have sufficient dimensionality to act as separatrices, partitioning energy surfaces into regions of qualitatively distinct behavior. This NHIM forms the natural (dynamical) equator of a (spherical) \emph{dividing surface} which locally divides an energy surface into two components (`reactants' and `products'), one on either side of the bottleneck. This dividing surface has all the desired properties sought for in \emph{transition state theory} where reaction rates are computed from the flux through a dividing surface. In fact, the dividing surface that we construct is crossed exactly once by reactive trajectories, and not crossed by nonreactive trajectories, and related to these properties, minimizes the flux upon variation of the dividing surface. We discuss three presentations of the energy surface and the phase space structures contained in it for 2-degree-of-freedom (DoF) systems in the threedimensional space $\R^3$, and two schematic models which capture many of the essential features of the dynamics for $n$-DoF systems. In addition, we elucidate the structure of the NHIM.Comment: 44 pages, 38 figures, PDFLaTe

Energy Landscape and Global Optimization for a Frustrated Model Protein

The three-color (BLN) 69-residue model protein was designed to exhibit frustrated folding. We investigate the energy landscape of this protein using disconnectivity graphs and compare it to a Go model, which is designed to reduce the frustration by removing all non-native attractive interactions. Finding the global minimum on a frustrated energy landscape is a good test of global optimization techniques, and we present calculations evaluating the performance of basin-hopping and genetic algorithms for this system.Comparisons are made with the widely studied 46-residue BLN protein.We show that the energy landscape of the 69-residue BLN protein contains several deep funnels, each of which corresponds to a different β-barrel structure

Spectral splitting photovoltaics using perovskite and wideband dye-sensitized solar cells

The extension of the light absorption of photovoltaics into the near-infrared region is important to increase the energy conversion efficiency. Although the progress of the lead halide perovskite solar cells is remarkable, and high conversion efficiency of >20% has been reached, their absorption limit on the long-wavelength side is similar to 800 nm. To further enhance the conversion efficiency of perovskite-based photovoltaics, a hybridized system with near-infrared photovoltaics is a useful approach. Here we report a panchromatic sensitizer, coded DX3, that exhibits a broad response into the near-infrared, up to similar to 1100 nm, and a photocurrent density exceeding 30 mA cm(-2) in simulated air mass 1.5 standard solar radiation. Using the DX3-based dye-sensitized solar cell in conjunction with a perovskite cell that harvests visible light, the hybridized mesoscopic photovoltaics achieved a conversion efficiency of 21.5% using a system of spectral splitting.open0

Evaluation of commercial soy sauce koji strains of Aspergillus oryzae for γ-aminobutyric acid (GABA) production

In this study, four selected commercial strains of Aspergillus oryzae were collected from soy sauce koji. These A. oryzae strains designated as NSK, NSZ, NSJ and NST shared similar morphological characteristics with the reference strain (A. oryzae FRR 1675) which confirmed them as A. oryzae species. They were further evaluated for their ability to produce γ-aminobutyric acid (GABA) by cultivating the spore suspension in a broth medium containing 0.4 % (w/v) of glutamic acid as a substrate for GABA production. The results showed that these strains were capable of producing GABA; however, the concentrations differed significantly (P < 0.05) among themselves. Based on the A. oryzae strains, highest GABA concentration was obtained from NSK (194 mg/L) followed by NSZ (63 mg/L), NSJ (51.53 mg/L) and NST (31.66 mg/L). Therefore, A. oryzae NSK was characterized and the sequence was found to be similar to A. oryzae and A. flavus with 99 % similarity. The evolutionary distance (K nuc) between sequences of identical fungal species was calculated and a phylogenetic tree prepared from the K nuc data showed that the isolate belonged to the A. oryzae species. This finding may allow the development of GABA-rich ingredients using A. oryzae NSK as a starter culture for soy sauce production

Quantum reaction boundary to mediate reactions in laser fields

Dynamics of passage over a saddle is investigated for a quantum system under the effect of time-dependent external field (laser pulse). We utilize the recently developed theories of nonlinear dynamics in the saddle region, and extend them to incorporate both time-dependence of the external field and quantum mechanical effects of the system. Anharmonic couplings and laser fields with any functional form of time dependence are explicitly taken into account. As the theory is based on the Weyl expression of quantum mechanics, interpretation is facilitated by the classical phase space picture, while no "classical approximation" is involved. We introduce a quantum reactivity operator to extract the reactive part of the system. In a model system with an optimally controlled laser field for the reaction, it is found that the boundary of the reaction in the phase space, extracted by the reactivity operator, is modulated with time by the effect of the laser field, to "catch" the system excited in the reactant region, and then to "release" it into the product region. This method provides new insights in understanding the origin of optimal control of chemical reactions by laser fields