Free Energy Gap Dependence of the Electron-Transfer Rate from the Inverted to the Normal Region

numerical study of the free energy gap (FEG) dependence of the electron-transfer rate in polar solvents is presented. This study is based on the generalized multidimensional hybrid model, which not only includes the solvent polarization and the molecular vibration modes, but also the biphasic polar response of the solvent. The free energy gap dependence is found to be sensitive to several factors, including the solvent relaxation rate, the electronic coupling between the surfaces, the frequency of the high-frequency quantum vibrational mode, and the magnitude of the solvent reorganization energy. It is shown that in some cases solvent relaxation can play an important role even in the Marcus normal regime. The minimal hybrid model involves a large number of parameters, giving rise to a diverse non-Marcus FEG behavior which is often determined collectively by these parameters. The model gives the linear free energy gap dependence of the logarithmic rate over a substantial range of FEG, spanning from the normal to the inverted regime. However, even for favorable values of the relevant parameters, a linear free energy gap dependence of the rate could be obtained only over a range of 5000-6000 cm(-1) (compared to the experimentally observed range of 10000 cm(-1) reported by Benniston et al.). The present work suggests several extensions/generalizations of the hybrid model which might be necessary to fully understand the observed free energy gap dependence.

A comparative study of multiple attribute tree and inverted file structures for large bibliographic files

A variety of data structures such as inverted file, multi-lists, quad tree, k-d tree, range tree, polygon tree, quintary tree, multidimensional tries, segment tree, doubly chained tree, the grid file, d-fold tree. super B-tree, Multiple Attribute Tree (MAT), etc. have been studied for multidimensional searching and related problems. Physical data base organization, which is an important application of multidimensional searching, is traditionally and mostly handled by employing inverted file. This study proposes MAT data structure for bibliographic file systems, by illustrating the superiority of MAT data structure over inverted file. Both the methods are compared in terms of preprocessing, storage and query costs. Worst-case complexity analysis of both the methods, for a partial match query, is carried out in two cases: (a) when directory resides in main memory, (b) when directory resides in secondary memory. In both cases, MAT data structure is shown to be more efficient than the inverted file method. Arguments are given to illustrate the superiority of MAT data structure in an average case also. An efficient adaptation of MAT data structure, that exploits the special features of MAT structure and bibliographic files, is proposed for bibliographic file systems. In this adaptation, suitable techniques for fixing and ranking of the attributes for MAT data structure are proposed. Conclusions and proposals for future research are presented.

Inverted slot-mode slow-wave structures for traveling-wave tubes

The dispersion and impedance characteristics of an inverted slot-mode (ISM) slow-wave structure computed by three different techniques, i.e., an analytical model based on a periodic quasi-TEM approach, an equivalent-circuit model, and 3-D electromagnetic simulation are obtained and compared. The comparison was carried out for three different slot-mode structures at S-, C-, and X-bands. The approach was also validated with experimental measurements on a practical X-band ISM traveling-wave tube. The design of ferruleless ISM slow-wave structures, both in circular and rectangular formats, has also been proposed and the predicted dispersion characteristics for these two geometries are compared with 3-D simulation and cold-test measurements. The impedance characteristics for all three designs are also compared.

Inverted V-Notch: Practical Proportional Weir

This paper presents a practical linear proportional weir of simple geometric shape in the form of an inverted V-notch or inward trapezium. The flow through this weir, of half-width w and altitude d, for depths above 0.22d is proportional to the depth of flow measured above a reference plane situated at 0.08d for all heads in the range 0.22d<=h<=0.94d, with a maximum percentage deviation of ±1.5 from the theoretical discharge. The linear relationship between head and discharge is based on numerical optimization procedures. Nearly 75% of the depth of inverted V-notch can be used effectively as the measuring range. Experiments with four weirs, with different vertex angles, show excellent agreement with the theory by giving an average coefficient of discharge for each weir varying from 0.61–0.62.

The C-Terminal Domain of the MutL Homolog from Neisseria gonorrhoeae Forms an Inverted Homodimer

The mismatch repair (MMR) pathway serves to maintain the integrity of the genome by removing mispaired bases from the newly synthesized strand. In E. coli, MutS, MutL and MutH coordinate to discriminate the daughter strand through a mechanism involving lack of methylation on the new strand. This facilitates the creation of a nick by MutH in the daughter strand to initiate mismatch repair. Many bacteria and eukaryotes, including humans, do not possess a homolog of MutH. Although the exact strategy for strand discrimination in these organisms is yet to be ascertained, the required nicking endonuclease activity is resident in the C-terminal domain of MutL. This activity is dependent on the integrity of a conserved metal binding motif. Unlike their eukaryotic counterparts, MutL in bacteria like Neisseria exist in the form of a homodimer. Even though this homodimer would possess two active sites, it still acts a nicking endonuclease. Here, we present the crystal structure of the C-terminal domain (CTD) of the MutL homolog of Neisseria gonorrhoeae (NgoL) determined to a resolution of 2.4 A. The structure shows that the metal binding motif exists in a helical configuration and that four of the six conserved motifs in the MutL family, including the metal binding site, localize together to form a composite active site. NgoL-CTD exists in the form of an elongated inverted homodimer stabilized by a hydrophobic interface rich in leucines. The inverted arrangement places the two composite active sites in each subunit on opposite lateral sides of the homodimer. Such an arrangement raises the possibility that one of the active sites is occluded due to interaction of NgoL with other protein factors involved in MMR. The presentation of only one active site to substrate DNA will ensure that nicking of only one strand occurs to prevent inadvertent and deleterious double stranded cleavage.

Improved Inverted V-Notch or Chimney Weir

This paper is devoted to the improvement of the measuring range of inverted V-notch (IVN) weir, a practical linear sharp-crested weir, designed earlier by the writers. The range of linearity of IVN can be considerably enhanced (by more than 200%) by the addition of a retangular weir of width 0.265W (W = half crest width) at a depth of 0.735d (d = altitude of IVN), above the crest of the weir, which is equivalent to providing at this depth two vertical straight lines to the IVN, resulting in a chimney-shaped profile; hence, the modified weir is named chimney weir. The design parameters of the weir, that is, the linearity range, base flow depth, and datum constant, which fixes the reference plane of the weir, are estimated by solving the nonlinear programming problem using a numerical optimization procedure. For flows through this weir above a depth of 0.22d, the discharges are proportional to the depth of flow measured above a reference plane situated at 0.08d above the weir crest for all heads in the range 0.22d <= h <= 2.43d, within a maximum percentage deviation of ±1.5 from the theoretical discharge. A significant result of the analysis is that the same linear head-discharge relationship governing the flow through the IVN is also valid for the extended chimney weir. Experiments with three different chimney weirs show excellent agreement with the theory by giving a constant average coefficient of discharge for each weir.

Electron transfer reaction in the marcus inverted region: role of high frequency vibrational modes

A theoretical study of the dynamics of photo-electron transfer reactions in the Marcus inverted regime is presented. This study is motivated partly by the recent proposal of Barbara et al. (J. Phys. Chem. 96, 3728, 1991) that a minimal model of an electron transfer reaction should consist of a polar solvent mode (X), a low frequency vibrational mode (Q) and one high frequency mode (q). Interplay between these modes may be responsible for the crossover observed in the dynamics from a solvent controlled to a vibrational controlled electron transfer. The following results have been obtained. (i) In the case of slowly relaxing solvents, the proximity of the point of excitation to an effective sink on the excited surface is critical in determining the decay of the reactant population. This is because the Franck-Condon overlap between the reactant ground and the product excited states decreases rapidly with increase in the quantum number of the product vibrational state. (ii) Non-exponential solvation dynamics has an important effect in determining the rates of electron transfer. Especially, a biphasic solvation and a large coupling between the reactant and the product states both may be needed to explain the experimental results. ©1996 American Institute of Physics

Quantum and non-Markovian effects in the electron transfer reaction dynamics in the Marcus inverted region

Electron transfer reactions in large molecules may often be coupled to both the polar solvent modes and the intramolecular vibrational modes of the molecule. This can give rise to a complex dynamics which may in some systems, like betaine, be controlled more by vibrational rather than by solvent effects. Additionally, a significant contribution from an ultrafast relaxation component in the solvation dynamics may enhance the complexity. To explain the wide range of behavior that has been observed experimentally, Barbara et al. recently proposed that a model of an electron transfer reaction should minimally consist of a low-frequency classical solvent mode (X), a low-frequency vibrational mode (Q), and a high-frequency quantum mode (q) (J. Phys. Chem. 1991, 96, 3728). In the present work, a theoretical study of this model is described. This study generalizes earlier work by including the biphasic solvent response and the dynamics of the low-frequency vibrational mode in the presence of a delocalized, extended reaction zone. A novel Green's function technique has been developed which allowed us to study the non-Markovian dynamics on a multidimensional surface. The contributions from the high-frequency vibrational mode and the ultrafast component in the non-Markovian solvent dynamics are found to be primarily responsible for the dramatic increase in charge transfer rate over the prediction of the classical theories that neglect both these factors. These, along with a large coupling between the reactant and the product states, may combine to render the electron transfer rate both very large and constant over a wide range of solvent relaxation rates. A study on the free energy gap dependence of the electron transfer rate reveals that the rates are sensitive to changes in the quantum frequency particularly when the free energy gap is very large.

Self-Assembled, Aligned ZnO Nanorod Buffer Layers for High-Current-Density, Inverted Organic Photovoltaics

Two different soft-chemical, self-assembly-based solution approaches are employed to grow zinc oxide (ZnO) nanorods with controlled texture. The methods used involve seeding and growth on a substrate. Nanorods with various aspect ratios (1-5) and diameters (15-65 nm) are grown. Obtaining highly oriented rods is determined by the way the substrate is mounted within the chemical bath. Furthermore, a preheat and centrifugation step is essential for the optimization of the growth solution. In the best samples, we obtain ZnO nanorods that are almost entirely oriented in the (002) direction; this is desirable since electron mobility of ZnO is highest along this crystallographic axis. When used as the buffer layer of inverted organic photovoltaics (I-OPVs), these one-dimensional (1D) nanostructures offer: (a) direct paths for charge transport and (b) high interfacial area for electron collection. The morphological, structural, and optical properties of ZnO nanorods are studied using scanning electron microscopy, X-ray diffraction, and ultraviolet-visible light (UV-vis) absorption spectroscopy. Furthermore, the surface chemical features of ZnO films are studied using X-ray photoelectron spectroscopy and contact angle measurements. Using as-grown ZnO, inverted OPVs are fabricated and characterized. For improving device performance, the ZnO nanorods are subjected to UV-ozone irradiation. UV-ozone treated ZnO nanorods show: (i) improvement in optical transmission, (ii) increased wetting of active organic components, and (iii) increased concentration of Zn-O surface bonds. These observations correlate well with improved device performance. The devices fabricated using these optimized buffer layers have an efficiency of similar to 3.2% and a fill factor of 0.50; this is comparable to the best I-OPVs reported that use a P3HT-PCBM active layer.

Oriented nanometric aggregates of partially inverted zinc ferrite: One-step processing and tunable high-frequency magnetic properties

In this work, it is demonstrated that the in situ growth of oriented nanometric aggregates of partially inverted zinc ferrite can potentially pave a way to alter and tune magnetocrystalline anisotropy that, in turn, dictates ferromagnetic resonance frequency (f(FMR)) by inducing strain due to aggregation. Furthermore, the influence of interparticle interaction on magnetic properties of the aggregates is investigated. Mono-dispersed zinc ferrite nanoparticles (<5 nm) with various degrees of aggregation were prepared through decomposition of metal-organic compounds of zinc (II) and iron (III) in an alcoholic solution under controlled microwave irradiation, below 200 degrees C. The nanocrystallites were found to possess high degree of inversion (>0.5). With increasing order of aggregation in the samples, saturation magnetization (at 5 K) is found to decrease from 38 emu/g to 24 emu/g, while coercivity is found to increase gradually by up to 100% (525 Oe to 1040 Oe). Anisotropy-mediated shift of f(FMR) has also been measured and discussed. In essence, the result exhibits an easy way to control the magnetic characteristics of nanocrystalline zinc ferrite, boosted with significant degree of inversion, at GHz frequencies. (C) 2015 AIP Publishing LLC.

Speaker verification based on the fusion of speech acoustics and inverted articulatory signals

We propose apractical, feature-level and score-level fusion approach by combining acoustic and estimated articulatory information for both text independent and text dependent speaker verification. From a practical point of view, we study how to improve speaker verification performance by combining dynamic articulatory information with the conventional acoustic features. On text independent speaker verification, we find that concatenating articulatory features obtained from measured speech production data with conventional Mel-frequency cepstral coefficients (MFCCs) improves the performance dramatically. However, since directly measuring articulatory data is not feasible in many real world applications, we also experiment with estimated articulatory features obtained through acoustic-to-articulatory inversion. We explore both feature level and score level fusion methods and find that the overall system performance is significantly enhanced even with estimated articulatory features. Such a performance boost could be due to the inter-speaker variation information embedded in the estimated articulatory features. Since the dynamics of articulation contain important information, we included inverted articulatory trajectories in text dependent speaker verification. We demonstrate that the articulatory constraints introduced by inverted articulatory features help to reject wrong password trials and improve the performance after score level fusion. We evaluate the proposed methods on the X-ray Microbeam database and the RSR 2015 database, respectively, for the aforementioned two tasks. Experimental results show that we achieve more than 15% relative equal error rate reduction for both speaker verification tasks. (C) 2015 Elsevier Ltd. All rights reserved.

Physical constraints, fundamental limits, and optimal locus of operating points for an inverted pendulum based actuated dynamic walker

The inverted pendulum is a popular model for describing bipedal dynamic walking. The operating point of the walker can be specified by the combination of initial mid-stance velocity (v(0)) and step angle (phi(m)) chosen for a given walk. In this paper, using basic mechanics, a framework of physical constraints that limit the choice of operating points is proposed. The constraint lines thus obtained delimit the allowable region of operation of the walker in the v(0)-phi(m) plane. A given average forward velocity v(x,) (avg) can be achieved by several combinations of v(0) and phi(m). Only one of these combinations results in the minimum mechanical power consumption and can be considered the optimum operating point for the given v(x, avg). This paper proposes a method for obtaining this optimal operating point based on tangency of the power and velocity contours. Putting together all such operating points for various v(x, avg,) a family of optimum operating points, called the optimal locus, is obtained. For the energy loss and internal energy models chosen, the optimal locus obtained has a largely constant step angle with increasing speed but tapers off at non-dimensional speeds close to unity.