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991.
The Effect of Alcohol and Carbonyl Functional Groups on the Competition between Unimolecular Decomposition and Isomerization in C4 and C5 Alkoxy Radicals
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Presented here are computed rates for the thermal unimolecular decomposition of a variety of alkoxy radicals with four‐ and five‐carbon length backbones. Three classes of molecules are examined: alkoxy radicals with saturated hydrocarbon backbones, those with alcohol functional groups, and those with carbonyl functional groups. The chosen species represent many of those found during the combustion of fossil fuels as well as bio‐derived alternatives. Density functional theory calculations were benchmarked against higher level coupled cluster calculations and used to explore the potential energy surfaces of these systems. Transition state theory was used to calculate high‐pressure limit rate coefficients of all radical intermediates in the regimes relevant to atmospheric chemistry and combustion. We show that the assumption that alkoxy radicals quickly decompose via β‐scission to aldehydes and other radicals is not valid for some of the alkoxy radicals investigated in this work. We further illustrate how intra‐H migrations in larger alkoxy radicals with carbonyl and alcohol functional groups can dominate unimolecular decomposition under combustion and atmospheric relevant conditions. Finally, we discuss why carbonyl groups can increase or decrease intra‐H migration barriers depending on their location relative to the transferring H‐atom. 相似文献
992.
Dr. Flávio Figueira Igor Marques Dr. Andreia S. F. Farinha Prof. Dr. Augusto C. Tomé Prof. Dr. José A. S. Cavaleiro Prof. Dr. Artur M. S. Silva Prof. Dr. Jonathan Sessler Prof. Dr. Vítor Félix Prof. Dr. João P. C. Tomé 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(40):14349-14355
A novel sapphyrin derivative was obtained from the reaction between a free‐base sapphyrin and dimethyl acetylenedicarboxylate (DMAD). The formation of the new compound involved a double aza‐Michael addition of two pyrrolic NH groups to a DMAD molecule, with the formation of a disubstituted ethano bridge. The NMR spectral data reveal a product with an unsymmetrical structure; DFT calculations provided support for a structure in which the ethano bridge links two adjacent pyrrole units. The present study provides a seemingly unprecedented example of an N,N′‐dinucleophile reacting with DMAD to form a heterocyclic compound in which the two N‐atoms are linked to the two sp3 carbon atoms derived from a substituted acetylene. 相似文献
993.
William A. Roughead Donald P. Miller Alfred D. French 《Journal of Macromolecular Science: Physics》2013,52(1-4):229-245
The previous Polymer Diffraction Symposium saw the use of x-ray film data array calculations to obtain diffraction intensities with computed accuracies. Subsequently, methods for geometrical deconvolution of overlapped diffraction spots have been developed. The techniques have now been applied to data arrays from films of Fortisan. Severely overlapped reflection arcs were splined and transformed into polar coordinate space, yielding orthogonalized diffraction spot groups. Spots were then identified 相似文献
994.
995.
Adult zebrafish as a model organism for behavioural genetics 总被引:1,自引:0,他引:1
Recent research has demonstrated the suitability of adult zebrafish to model some aspects of complex behaviour. Studies of
reward behaviour, learning and memory, aggression, anxiety and sleep strongly suggest that conserved regulatory processes
underlie behaviour in zebrafish and mammals. The isolation and molecular analysis of zebrafish behavioural mutants is now
starting, allowing the identification of novel behavioural control genes. As a result of this, studies of adult zebrafish
are now helping to uncover the genetic pathways and neural circuits that control vertebrate behaviour. 相似文献
996.
997.
Attila G. Császár Tamás Szidarovszky Nikolai F. Zobov Oleg L. Polyansky Jonathan Tennyson 《Journal of Quantitative Spectroscopy & Radiative Transfer》2010,111(9):1043-1106
A new, accurate, global, mass-independent, first-principles potential energy surface (PES) is presented for the ground electronic state of the water molecule. The PES is based on 2200 energy points computed at the all-electron aug-cc-pCV6Z IC-MRCI(8,2) level of electronic structure theory and includes the relativistic one-electron mass-velocity and Darwin corrections. For H216O, the PES has a dissociation energy of D0 = 41 109 cm−1 and supports 1150 vibrational energy levels up to 41 083 cm−1. The deviation between the computed and the experimentally measured energy levels is below 15 cm−1 for all the states with energies less than 39 000 cm−1. Characterization of approximate vibrational quantum numbers is performed using several techniques: energy decomposition, wave function plots, normal mode distribution, expectation values of the squares of internal coordinates, and perturbing the bending part of the PES. Vibrational normal mode labels, though often not physically meaningful, have been assigned to all the states below 26 500 cm−1 and to many more above it, including some highly excited stretching states all the way to dissociation. Issues to do with calculating vibrational band intensities for the higher-lying states are discussed. 相似文献
998.
The cathode–electrolyte interface in a solid oxide fuel cell is examined to understand why premature delamination is observed in alumina substituted YSZ electrolyte. From XRD, SEM and TEM observations it was concluded that after high temperature sintering a tetragonal (Mn,Al)3O4 forms at the interface, which during prolonged fuel cell operation forms a cubic (Mn,Al)3O4 phase. This transformation is associated with volume decrease creating voids which ultimately weaken the cathode–electrolyte interface sufficiently for the cathode layer to delaminate off the YSZ–Al2O3 electrolyte. 相似文献
999.
We calculate direct gaugino pair production at hadron colliders at next-to-leading order of perturbative QCD, resumming simultaneously large logarithms in the small transverse-momentum and threshold regions to next-to-leading logarithmic accuracy. Numerical predictions are presented for transverse momentum and invariant mass spectra as well as for total cross sections and compared to results obtained at fixed order and with pure transverse-momentum and threshold resummation. We find that our new results are in general in good agreement with the previous ones, but often even more precise. 相似文献
1000.
Matthew J. Hamer Jonathan A.D. Wattis Richard S. Graham 《ournal of non Newtonian Fluid Mechanics》2010,165(19-20):1294-1301
We present an analytically derived model for flow induced crystallization (FIC), based upon the recent Graham–Olmsted simulation. We use combinatorial techniques to calculate nucleation energy landscapes, which correctly predict simulation data. Applying both the analytic calculation and the simulation, we put forward a simple expression relating nucleation rate to polymer chain stretch. We also investigate bimodal blends, an important step to understanding polydisperse systems and eventually modeling industrial polymer melts. 相似文献