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.

Evolution of mosaic structure in InN grown by metalorganic chemical vapor deposition

Mosaic structure in InN layers grown by metalorganic chemical vapor deposition at various temperatures has been investigated by X-ray diffraction (XRD). With a combination of Williamson-Hall measurement and fitting of twist angles, it was found that variation of growth temperature from 450 to 550 degrees C leads to the variation of the lateral coherence length, vertical coherence length, tilt and twist of mosaic blocks in InN films in a, respectively, monotonic way. In particular, mosaic tilt increases whereas mosaic twist decreases with elevating temperature. Atomic force microscopy shows the morphological difference of the InN nucleation layers grown at 450 and 550 degrees C. Different coalescence thickness and temperature-dependent in-plane rotation of InN nuclei are considered to account for the XRD results. (c) 2006 Elsevier B.V. All rights reserved.

Deltack, Blanket Study

There are two objectives of this study.The first one was to study the new instrument Deltack fromPrufbau, and with the new knowledge, study the interaction between blanket and paper.Deltack is a new instrument to measure the ink splitting force. Blankets from an earlier study doneby GATF have been montered on 12 different Deltack print forms and those have together with Deltackbeen the base for this project.This study together with information from GATF’s study shows that some of the blankets have ahigher capability to adsorb ink. Those blankets generate a sharper shape on the force curve, they havea lower dot gain, but they print not as good solid.

Two forms of Pf1 Inovirus: X-ray diffraction studies on a structural phase transition and a calculated libration normal mode of the asymmetric unit

Inovirus is a helical array of alpha-helical protein asymmetric units surrounding a DNA core. X-ray fibre diffraction studies show that the Pf1 species of Inovirus can undergo a reversible temperature-induced transition between two similar structural forms having slightly different virion helix parameters. Molecular models of the two forms show no evidence for altered interactions between the protein and either the solvent or the viral DNA; but there are significant differences in the shape and orientation of the protein asymmetric unit, related to the changes in the virion parameters. Normal modes involving libration of whole asymmetric units are in a frequency range with appreciable entropy of libration, and the structural transition may be related to changes in libration.

Two forms of PF1 INOVIRUS: X-ray diffraction studies on a structural phase transition and a calculated libration normal mode of the assymetric unit

Inovirus is a helical array of agr-helical protein asymmetric units surrounding a DNA core. X-ray fibre diffraction studies show that the Pf1 species of Inovirus can undergo a reversible temperature-induced transition between two similar structural forms having slightly different virion helix parameters. Molecular models of the two forms show no evidence for altered interactions between the protein and either the solvent or the viral DNA; but there are significant differences in the shape and orientation of the protein asymmetric unit, related to the changes in the virion parameters. Normal modes involving libration of whole asymmetric units are in a frequency range with appreciable entropy of libration, and the structural transition may be related to changes in libration.

Mode-specific chemisorption of CH4 on Pt{110}-(1 x 2) explored by first-principles molecular dynamics

The chemisorption of CH4 on Pt{110}-(1 x 2) has been studied by vibrational analysis of the reaction pathway defined by the potential energy surface and, in time reversal, by first-principles molecular dynamics simulations of CH4 associative desorption, with the electronic structure treated explicitly using density functional theory. We find that the symmetric stretch vibration ν1 is strongly coupled to the reaction coordinate; our results therefore provide a firm theoretical basis for recently reported state-resolved reactivity measurements, which show that excitation of the ν1 normal mode is the most efficient way to enhance the reaction probability

Genotype x location x feeding interactions in Nellore cattle calculated through three-mode principal component analysis

The main objective of this study was to apply three-mode principal component analysis to assess the triple interaction (genotype x location x feeding) on direct genetic value for weight at 205 days of age. We used 60 sires with offspring in three regions of northeastern Brazil (Maranhao, Mata and Agreste, and Reconcavo Baiano) and raised on a pasture regime or with supplementation. There was no interaction between genotype and location, but there was a correlation between genotype and direct effect of feeding. The use of sires should be dictated according to the system of rearing of their offspring.

Measurement of the oscillation frequency of B s mesons in the hadronic decay mode B s pi D s (phi pi) X with the D0 detector at the Fermilab Tevatron collider

The standard model (SM) of particle physics is a theory, describing three out of four fundamental forces. In this model the Cabibbo-Kobayashi-Maskawa (CKM) matrix describes the transformation between the mass and weak eigenstates of quarks. The matrix properties can be visualized as triangles in the complex plane. A precise measurement of all triangle parameters can be used to verify the validity of the SM. The least precisely measured parameter of the triangle is related to the CKM element |Vtd|, accessible through the mixing frequency (oscillation) of neutral B mesons, where mixing is the transition of a neutral meson into its anti-particle and vice versa. It is possible to calculate the CKM element |Vtd| and a related element |Vts| by measuring the mass differences Dmd (Dms ) between neutral Bd and bar{Bd} (Bs and bar{Bs}) meson mass eigenstates. This measurement is accomplished by tagging the initial and final state of decaying B mesons and determining their lifetime. Currently the Fermilab Tevatron Collider (providing pbar{p} collisions at sqrt{s}=1.96 TeV) is the only place, where Bs oscillations can be studied. The first selection of the "golden", fully hadronic decay mode Bs->Ds pi(phi pi)X at DØ is presented in this thesis. All data, taken between April 2002 and August 2007 with the DØ detector, corresponding to an integrated luminosity of int{L}dt=2.8/fb is used. The oscillation frequency Dms and the ratio |Vtd|/|Vts| are determined as Dms = (16.6 +0.5-0.4(stat) +0.4-0.3(sys)) 1/ps, |Vtd|/|Vts| = 0.213 +0.004-0.003(exp)pm 0.008(theor). These results are consistent with the standard model expectations and no evidence for new physics is observable.

73.7 Tb/s (96 x 3 x 256-Gb/s) mode-division-multiplexed DP-16QAM transmission with inline MM-EDFA

Transmission of a 73.7 Tb/s (96x3x256-Gb/s) DP-16QAM mode-division-multiplexed signal over 119km of few-mode fiber transmission line incorporating an inline multi mode EDFA and a phase plate based mode (de-)multiplexer is demonstrated. Data-aided 6x6 MIMO digital signal processing was used to demodulate the signal. The total demonstrated net capacity, taking into account 20% of FEC-overhead and 7.5% additional overhead (Ethernet and training sequences), is 57.6 Tb/s, corresponding to a spectral efficiency of 12 bits/s/Hz.

Full-field electronic dispersion compensation of a 10 Gbit/s OOK signal over 4 x 124 km field-installed single-mode fibre

We experimentally demonstrate the use of full-field electronic dispersion compensation (EDC) to achieve a bit error rate of 5 x 10(-5) at 22.3 dB optical signal-to-noise ratio for single-channel 10 Gbit/s on-off keyed signal after transmission over 496 km field-installed single-mode fibre with an amplifier spacing of 124 km. This performance is achieved by designing the EDC so as to avoid electronic amplification of the noise content of the signal during full-field reconstruction. We also investigate the tolerance of the system to key signal processing parameters, and numerically demonstrate that single-channel 2160 km single mode fibre transmission without in-line optical dispersion compensation can be achieved using this technique with 80 km amplifier spacing and optimized system parameters.

73.7 Tb/s (96 x 3 x 256-Gb/s) mode-divisionmultiplexed DP-16QAM transmission with inline MM-EDFA

Transmission of a 73.7 Tb/s (96x3x256-Gb/s) DP-16QAM mode-division- multiplexed signal over 119km of few-mode fiber transmission line incorporating an inline multi mode EDFA and a phase plate based mode (de-)multiplexer is demonstrated. Data-aided 6x6 MIMO digital signal processing was used to demodulate the signal. The total demonstrated net capacity, taking into account 20% of FEC-overhead and 7.5% additional overhead (Ethernet and training sequences), is 57.6 Tb/s, corresponding to a spectral efficiency of 12 bits/s/Hz. © 2012 Optical Society of America.

Scale-dependent fracture mode in Cu-Ni laminate composites

Fracture behavior of Cu-Ni laminate composites has been investigated by tensile testing. It was found that as the individual layer thickness decreases from 100 to 20nm, the resultant fracture angle of the Cu-Ni laminate changes from 72 degrees to 50 degrees. Cross-sectional observations reveal that the fracture of the Ni layers transforms from opening to shear mode as the layer thickness decreases while that of the Cu layers keeps shear mode. Competition mechanisms were proposed to understand the variation in fracture mode of the metallic laminate composites associated with length scale.

Comparing exercise prescribed with exercise completed : effects of gender and mode of exercise

The purpose of this study was to compare the amount of exercise prescribed with the amount completed between two different modes of training intervention and between the sexes. Thirty-two men (mean age = 39.1 years, body mass index = 32.9 kg · m-2) and women (mean age = 39.6 years, body mass index = 32.1 kg · m-2) were prescribed traditional resistance training or light-resistance circuit training for 16 weeks. Lean mass and fat mass were determined by dual-energy X-ray absorptiometry at weeks 1 and 16. A completion index was calculated to provide a measure of the extent to which participants completed exercise training relative to the amount of exercise prescribed. The absolute amount of exercise completed by the circuit training group was significantly greater than the amount prescribed (P < 0.0001). The resistance training group consistently under-completed relative to the amount prescribed, but the difference was not significant. The completion index for the circuit training group (26 ± 21.7%) was significantly different from that of the resistance training group (-7.4 ± 3.0%). The completion index was not significantly different between men and women in either group. These data suggest that overweight and obese individuals participating in light-resistance circuit training complete more exercise than is prescribed. Men and women do not differ in the extent to which they over- or under-complete prescribed exercise.