Bond-forming reactions of N22+ with C2H4, C2H6, C3H4 and C3H6

Mass spectrometry, coupled with position-sensitive coincidence detection, has been used to investigate the reactions of N22+ with various small hydrocarbon molecules (C2H4, C2H6, C3H4, c-C3H6 and n-C3H6) at collision energies below 10 eV in the centre-of-mass frame. The reactivity, in each case, is dominated by electron transfer. However, in each collision system we also clearly identify products formed following the creation of new chemical bonds. These bond-forming reactions comprise two distinct classes: (i) hydride transfer reactions which initially form NnH+ (n = 1, 2) and (ii) N+ transfer reactions which form monocationic products with Csingle bondN bonds. These bond-forming reactions make a small (5–10%), but significant, contribution to the overall product ion yield in each collision system. The temporal and positional data recorded by our coincidence detection technique are used to construct scattering diagrams which reveal the mechanisms of the bond-forming reactions. For the hydride transfer process, the scattering diagrams reveal that H− is directly transferred from the hydrocarbon to N22+ at significant interspecies separations. For the hydride transfer reactions with C2H4, C2H6 and C3H4, we observe fragmentation of the nascent N2H+* to form NH+ + N. The N+ transfer reaction also proceeds by a direct mechanism: a single step involving N+/H exchange results in the formation of a singly-charged organic species containing a Csingle bondN bond which is detected in coincidence with H+. The two general classes of bond-forming reactivity we observe in the reactions of N22+ with organic molecules may be relevant in the chemistry of energised environments rich in molecular nitrogen and hydrocarbon species, such as the atmosphere of Titan

Controlling electron emission from the photoactive yellow protein chromophore by substitution at the coumaric acid group

Understanding how the interactions between a chromophore and its surrounding protein control the function of a photoactive protein remains a challenge. Here, we present the results of photoelectron spectroscopy measurements and quantum chemistry calculations aimed at investigating how substitution at the coumaryl tail of the photoactive yellow protein chromophore controls competing relaxation pathways following photoexcitation of isolated chromophores in the gas phase with ultraviolet light in the range 350-315 nm. The photoelectron spectra are dominated by electrons resulting from direct detachment and fast detachment from the 2(1)ππ* state but also have a low electron kinetic energy component arising from autodetachment from lower lying electronically excited states or thermionic emission from the electronic ground state. We find that substituting the hydrogen atom of the carboxylic acid group with a methyl group lowers the threshold for electron detachment but has very little effect on the competition between the different relaxation pathways, whereas substituting with a thioester group raises the threshold for electron detachment and appears to 'turn off' the competing electron emission processes from lower lying electronically excited states. This has potential implications in terms of tuning the light-induced electron donor properties of photoactive yellow protein

A photoelectron imaging and quantum chemistry study of the deprotonated indole anion

Indole is an important molecular motif in many biological molecules and exists in its deprotonated anionic form in the cyan fluorescent protein, an analogue of green fluorescent protein. However, the electronic structure of the deprotonated indole anion has been relatively unexplored. Here, we use a combination of anion photoelectron velocity-map imaging measurements and quantum chemistry calculations to probe the electronic structure of the deprotonated indole anion. We report vertical detachment energies (VDEs) of 2.45 ± 0.05 eV and 3.20 ± 0.05 eV, respectively. The value for D₀ is in agreement with recent high-resolution measurements whereas the value for D₁ is a new measurement. We find that the first electronically excited singlet state of the anion, S₁(ππ*), lies above the VDE and has shape resonance character with respect to the D₀ detachment continuum and Feshbach resonance character with respect to the D₁ continuum

A Utility-Based Approach to Bandwidth Allocation and Link Scheduling in Wireless Networks

We study the problem of optimizing aggregate user utility in wireless ad-hoc networks under the constraints of wireless interference. We develop a market-oriented approach to bandwidth allocation with a tˆatonnement process and demonstrate its ability to effectively price bottleneck resource. One novelty is that we choose to price “interference goods” to capture the externality imposed by one application’s use of the network on other applications. In making progress we also propose a modification to the CSMA protocol that is robust enough to handle a non-schedulable bandwidth schedule. Experimental results on simulated network topologies show that the market-based approach has better scalability than alternate approximation methods and is much more efficient in terms of runtime.Engineering and Applied Science

Constraints on Finite Soft Supersymmetry-Breaking Terms

Requiring the soft supersymmetry-breaking (SSB) parameters in finite gauge-Yukawa unified models to be finite up to and including two-loop order, we derive a two-loop sum rule for the soft scalar-masses. It is shown that this sum rule coincides with that of a certain class of string models in which the massive string states are organized into N=4 supermultiplets. We investigate the SSB sector of two finite SU(5) models. Using the sum rule which allows the non-universality of the SSB terms and requiring that the lightest superparticle particleis neutral, we constrain the parameter space of the SSB sector in each model.Comment: 34 page

Explicit and Exact Solutions to a Kolmogorov-Petrovskii-Piskunov Equation

Some explicit traveling wave solutions to a Kolmogorov-Petrovskii-Piskunov equation are presented through two ans\"atze. By a Cole-Hopf transformation, this Kolmogorov-Petrovskii-Piskunov equation is also written as a bilinear equation and further two solutions to describe nonlinear interaction of traveling waves are generated. B\"acklund transformations of the linear form and some special cases are considered.Comment: 14pages, Latex, to appear in Intern. J. Nonlinear Mechanics, the original latex file is not complet