Photolysis of Diborane at 1849 Å

The photolysis of diborane at 1849 Å has been studied in a specially constructed, internal‐type mercury‐vapor lamp. The products have been found to be H_2, B_(4)H_(10), B_(5)H_(11), and, at low pressures, a —BH— polymer. Reaction orders at 4°C have been obtained from linear plots of reaction products vs time for a range of diborane pressures from 0.08 to 80 cm, and at two light intensities. Linear relations between products and time existed only at very low conversions (∼1%), which required the development of a low‐temperature separation method for manipulating and analyzing the traces of B_(4)H_(10) and B_(5)H_(11). Because of the reactivity of these compounds, a detailed conditioning procedure was employed for the glass system. A mechanism consistant with the kinetic data and suggested by the kinetic results of thermal and photosensitized decomposition of diborane is postulated: the B_(5)H_(11) is assumed to be formed from a dissociation of B_(2)H_6 into BH_3's, the latter arising from an excited molecule. The B_(4)H_(10) and polymer are assumed to be formed from a dissociation of B_(2)H_6 into B_(2)H_5 and H, followed by radical recombination. There is a significant difference between the kinetics of thermal and photochemical B_(5)H_(11) formation, a result which may be due to the considerable energy excess of the 1849 quantum over that needed for dissociation (∼125‐kcal excess). These kinetic results raise a number of interesting questions, questions which can only be resolved through further investigations of effects due to light intensity, added inert gases, and temperature. The primary quantum yield of the step forming B_(2)H_5 and H is about 10 times higher than that of the one forming BH_3's. A rather rough estimate suggests that the former is of the order of magnitude of unity

An intramolecular theory of the mass-independent isotope effect for ozone. II. Numerical implementation at low pressures using a loose transition state

A theory is described for the variation in the rate constants for formation of different ozone isotopomers from oxygen atoms and molecules at low pressures. The theory is implemented using a simplified description which treats the transition state as loose. The two principal features of the theory are a phase space partitioning of the transition states of the two exit channels after formation of the energetic molecule and a small (ca. 15%) decrease in the effective density of states, rho [a "non-Rice–Ramsperger–Kassel–Marcus (RRKM) effect"], for the symmetric ozone isotopomers [B. C. Hathorn and R. A. Marcus, J. Chem. Phys. 111, 4087 (1999)]. This decrease is in addition to the usual statistical factor of 2 for symmetric molecules. Experimentally, the scrambled systems show a "mass-independent" effect for the enrichments delta (for trace) and E (for heavily) enriched systems, but the ratios of the individual isotopomeric rate constants for unscrambled systems show a strongly mass-dependent behavior. The contrasting behavior of scrambled and unscrambled systems is described theoretically using a "phase space" partitioning factor. In scrambled systems an energetic asymmetric ozone isotopomer is accessed from both entrance channels and, as shown in paper I, the partitioning factor becomes unity throughout. In unscrambled systems, access to an asymmetric ozone is only from one entrance channel, and differences in zero-point energies and other properties, such as the centrifugal potential, determine the relative contributions (the partitioning factors) of the two exit channels to the lifetime of the resulting energetic ozone molecule. They are responsible for the large differences in individual recombination rate constants at low pressures. While the decrease in rho for symmetric systems is attributed to a small non-RRKM effect eta, these calculated results are independent of the exact origin of the decrease. The calculated "mass-independent" enrichments, delta and E, in scrambled systems are relatively insensitive to the transition state (TS), because of the absence of the partitioning factor in their case (for a fixed non-RRKM eta). They are compared with the data at room temperature. Calculated results for the ratios of individual isotopomeric rate constants for the strongly mass-independent behavior for unscrambled systems are quite sensitive to the nature of the TS because of the partitioning effect. The current data are available only at room temperature but the loose TS is valid only at low temperatures. Accordingly, the results calculated for the latter at 140 K represent a prediction, for any given eta. At present, a comparison of the 140 K results can be made only with room temperature data. They show the same trends as, and are in fortuitous agreement, with the data. Work is in progress on a description appropriate for room temperature

Cluster algebras in scattering amplitudes with special 2D kinematics

We study the cluster algebra of the kinematic configuration space $Conf_n(\mathbb{P}^3)$ of a n-particle scattering amplitude restricted to the special 2D kinematics. We found that the n-points two loop MHV remainder function found in special 2D kinematics depend on a selection of \XX-coordinates that are part of a special structure of the cluster algebra related to snake triangulations of polygons. This structure forms a necklace of hypercubes beads in the corresponding Stasheff polytope. Furthermore in $n = 12$, the cluster algebra and the selection of \XX-coordinates in special 2D kinematics replicates the cluster algebra and the selection of \XX-coordinates of $n=6$ two loop MHV amplitude in 4D kinematics.Comment: 22 page

An intramolecular theory of the mass-independent isotope effect for ozone. I

An intramolecular theory of the unusual mass-independent isotope effect for ozone formation and dissociation is described. The experiments include the enrichment factor, its dependence on the ambient pressure, the ratio of the formation rates of symmetric and asymmetric ozone isotopomers, the enrichment of ozone formed from heavily enriched oxygen isotopes, the comparison of that enrichment to that when the heavy isotopes are present in trace amounts, the isotopic exchange rate constant, and the large mass-dependent effect when individual rate constants are measured, in contrast with the mass-independent effect observed for scrambled mixtures. To explain the results it is suggested that apart from the usual symmetry number ratio of a factor of 2, the asymmetric ozone isotopomers have a larger density of reactive (coupled) quantum states, compared with that for the symmetric isotopomers (about 10%), due to being more "RRKM-like" (Rice–Ramsperger–Kessel–Marcus): Symmetry restricts the number of intramolecular resonances and coupling terms in the Hamiltonian which are responsible for making the motion increasingly chaotic and, thereby, increasingly statistical. As a result the behavior occurs regardless of whether the nuclei are bosons (16O, 18O) or fermions (17O). Two alternative mechanisms are also considered, one invoking excited electronic states and the other invoking symmetry control in the entrance channel. Arguments against each are given. An expression is given relating the mass-independent rates of the scrambled systems to the mass-dependent rates of the unscrambled ones, and the role played by a partitioning term in the latter is described. Different definitions for the enrichment factor for heavily enriched isotopic systems are also considered. In the present paper attention is focused on setting up theoretical expressions and discussing relationships. They provide a basis for future detailed calculations

Coulomb-Modified Fano Resonance in a One-Lead Quantum Dot

We investigate a tunable Fano interferometer consisting of a quantum dot coupled via tunneling to a one-dimensional channel. In addition to Fano resonance, the channel shows strong Coulomb response to the dot, with a single electron modulating channel conductance by factors of up to 100. Where these effects coexist, lineshapes with up to four extrema are found. A model of Coulomb-modified Fano resonance is developed and gives excellent agreement with experiment.Comment: related papers available at http://marcuslab.harvard.ed

Visual analytics for supply network management: system design and evaluation

We propose a visual analytic system to augment and enhance decision-making processes of supply chain managers. Several design requirements drive the development of our integrated architecture and lead to three primary capabilities of our system prototype. First, a visual analytic system must integrate various relevant views and perspectives that highlight different structural aspects of a supply network. Second, the system must deliver required information on-demand and update the visual representation via user-initiated interactions. Third, the system must provide both descriptive and predictive analytic functions for managers to gain contingency intelligence. Based on these capabilities we implement an interactive web-based visual analytic system. Our system enables managers to interactively apply visual encodings based on different node and edge attributes to facilitate mental map matching between abstract attributes and visual elements. Grounded in cognitive fit theory, we demonstrate that an interactive visual system that dynamically adjusts visual representations to the decision environment can significantly enhance decision-making processes in a supply network setting. We conduct multi-stage evaluation sessions with prototypical users that collectively confirm the value of our system. Our results indicate a positive reaction to our system. We conclude with implications and future research opportunities.The authors would like to thank the participants of the 2015 Businessvis Workshop at IEEE VIS, Prof. Benoit Montreuil, and Dr. Driss Hakimi for their valuable feedback on an earlier version of the software; Prof. Manpreet Hora for assisting with and Georgia Tech graduate students for participating in the evaluation sessions; and the two anonymous reviewers for their detailed comments and suggestions. The study was in part supported by the Tennenbaum Institute at Georgia Tech Award # K9305. (K9305 - Tennenbaum Institute at Georgia Tech Award)Accepted manuscrip

Towards Developing an Online Social Media-based Mobile Learning System

The advancement of Information and Communication Technology (ICT) and the Internet revolution gave rise to the several learning technologies on the web and mobile platform. During the last decade, the social media network became available for users to socialise and collaborate among peer group. Hence, The integration of e-learning and social media using mobile device as access point is to allow for learning and collaboration anytime, anywhere. This study seeks to provide learning on the social network platform for users to view the application on a mobile device and also foster collaboration among scholars. The system was developed using an open source Content Management System (CMS) Wordpress and Buddypress running on a WAMP or XAMPP server. MySQL was used as database. The usability of the System on the different mobile devices used was evaluated by identifying the usability attributes; designing a questionnaire based on those attributes and then analyzing the results with Statistical Package for Social Science (SPSS). The results showed that the learning system had a good usability score on mobile device

Finite element analysis of fluid-filled elastic piping systems

Two finite element procedures are described for predicting the dynamic response of general 3-D fluid-filled elastic piping systems. The first approach, a low frequency procedure, models each straight pipe or elbow as a sequence of beams. The contained fluid is modeled as a separate coincident sequence axial members (rods) which are tied to the pipe in the lateral direction. The model includes the pipe hoop strain correction to the fluid sound speed and the flexibility factor correction to the elbow flexibility. The second modeling approach, an intermediate frequency procedure, follows generally the original Zienkiewicz-Newton scheme for coupled fluid-structure problems except that the velocity potential is used as the fundamental fluid unknown to symmetrize the coefficient matrices. From comparisons of the beam model predictions to both experimental data and the 3-D model, the beam model is validated for frequencies up to about two-thirds of the lowest fluid-filled labor pipe mode. Accurate elbow flexibility factors are seen to be crucial for effective beam modeling of piping systems