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91.
We report a full-dimensional potential energy surface (PES) for the OH+NO(2) reaction based on fitting more than 55,000 energies obtained with density functional theory-B3LYP6-311G(d,p) calculations. The PES is invariant with respect to permutation of like nuclei and describes all isomers of HOONO, HONO(2), and the fragments OH+NO(2) and HO(2)+NO. Detailed comparison of the structures, energies, and harmonic frequencies of various stationary points on the PES are made with previous and present high-level ab initio calculations. Two hydrogen-bond complexes are found on the PES and confirmed by new ab initio CASPT2 calculations. Quasiclassical trajectory calculations of the cross sections for ground rovibrational OH+NO(2) association reactions to form HOONO and HONO(2) are done using this PES. The cross section to form HOONO is larger than the one to form HONO(2) at low collision energies but the reverse is found at higher energies. The enhancement of the HOONO complex at low collision energies is shown to be due, in large part, to the transient formation of a H-bond complex, which decays preferentially to HOONO. The association cross sections are used to obtain rate constants for formation of HOONO and HONO(2) for the ground rovibrational states in the high-pressure limit. 相似文献
92.
An on-chip micropump for portable microfluidic applications was investigated using mathematical modeling and experimental testing. This micropump is activated by the addition of water, via a dropper, to ionic polymer particles that swell due to osmotic effects when wetted. The resulting particle volume increase deflects a membrane, forcing a separate fluid from an adjacent reservoir. The micropump components, along with the microfluidic components, are fabricated using the contact liquid photolithographic polymerization (CLiPP) method. The maximum flow rate achieved with this pump is 17 microL per minute per mg of dry polymer particles of 355-425 microm in diameter. The pump flow rate may be controlled by adjusting the particle size and amount, the membrane properties, and the channel dimensions. The experimental results demonstrate good agreement with an analytical model describing the particle swelling and its coupling with resistive forces from the bending membrane, viscous flow in the microchannel, and interfacial effects. Key features of this micropump are that it can be placed directly on a microdevice, and that it requires only a small amount of water and no external power supply to function. Therefore, this pumping system is useful for applications in which a highly portable device is required. 相似文献
93.
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95.
Michael Rhrig Eric L. Petersen David F. Davidson Ronald K. Hanson Craig T. Bowman 《国际化学动力学杂志》1997,29(10):781-789
The rate coefficient of the reaction CH+O2 → products was determined by measuring CH-radical concentration profiles in shock-heated 100–150 ppm ethane/1000 ppm O2 mixtures in Ar using cw, narrow-linewidth laser absorption at 431.131 nm. Comparing the measured CH concentration profiles to ones calculated using a detailed kinetics model, yielded the following average value for the rate coefficient independent of temperature over the range 2200–2600 K: The experimental conditions were chosen such that the calculated profiles were sensitive mainly to the reactions CH+O2 → products and CH3+M → CH+H2+M. For the methyl decomposition reaction channel, the following rate-coefficient expression provided the best fit of the measured CH profiles: Additionally, the rate coefficient of the reaction CH2+H→CH+ H2 was determined indirectly in the same system: © 1997 John Wiley & Sons, Inc. 相似文献
96.
Anandkumar R. Kannurpatti Karin J. Anderson Jay W. Anseth Christopher N. Bowman 《Journal of Polymer Science.Polymer Physics》1997,35(14):2297-2307
Crosslinked polymer networks are used in a wide variety of applications. To use these materials effectively, a fundamental understanding of their structural evolution and the relationship between material properties and structure is essential. In this article, a novel technique employing “iniferters,” i.e., living radical polymerizations, to photopolymerize these networks is utilized to study the property and structural evolution of these highly desirable materials. Living radical polymerizations are used in this work since this technique avoids the problem of carbon radical trapping encountered while using conventional initiators. Dynamic mechanical measurements are performed on highly crosslinked methacrylate networks to glean information regarding their structural heterogeneity. By performing these measurements on homopolymerized samples at various stages of the reaction and on copolymerized samples of multifunctional methacrylates, the mechanical properties are characterized as a function of double bond conversion and comonomer composition. From such analyses, with respect to both temperature and frequency, quantitative conclusions regarding the structure of the networks are drawn. This effort is aimed at exploiting the living radical polymerizations initiated by p-xylylene bis(N,N-diethyl dithiocarbamate) (XDT), to study the mechanical property evolution and structural heterogeneity of crosslinked polymers which is nearly impossible otherwise. Polymers examined in this study include networks formed by homopolymerization of diethylene glycol dimethacrylate (DEGDMA) and polyethylene glycol 600 dimethacrylate (PEG600DMA) as well as copolymers of DEGDMA and PEG600DMA. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35 : 2297–2307, 1997 相似文献
97.
Smith SD Hamersky MW Bowman MK Rasmussen KØ Spontak RJ 《Langmuir : the ACS journal of surfaces and colloids》2006,22(15):6465-6468
The conditions signaling the formation of bidisperse brushes in ordered block copolymers are investigated as an A(2) block is progressively grown onto an A(1)B diblock copolymer to form a series of molecularly asymmetric, isomorphic A(1)BA(2) triblock copolymers. Small-angle scattering and self-consistent field theory confirm that the microphase-ordered period decreases when the A(2) block is short relative to the A(1) block, but then increases as A(1)+A(2) bidisperse brushes develop. The mechanical properties systematically follow the spatial distribution of the A(2) block. 相似文献
98.
Bowman WR Burchell CJ Kilian P Slawin AM Wormald P Woollins JD 《Chemistry (Weinheim an der Bergstrasse, Germany)》2006,12(24):6366-6381
The synthesis and full characterisation of a series of 1,2,4-thiadiazoles is reported. (SCN)(x) has been studied by a variety of techniques and the data compared with 1,2,4-thiadiazole and 1,2,4-dithiazoles. The observed data suggest that the polymer consists of 1,2,4-dithiazole rings linked by nitrogen atoms. For (SCN)(x), the MALDI-TOF mass spectroscopy showed a parent ion at 1149 and a series of peaks with (SCN)(2) repeat units (116 m/z); this result implies that (SCN)(2) may be the monomer unit of the polymer. Its IR spectrum shows a very broad peak with maximum at 1134 cm(-1) consisting of several overlapping peaks in the same region as ring vibrations for 1,2,4-thiadiazole and 1,2,4-dithiazole compounds. Peaks in the Raman spectrum in the range 400-480 cm(-1) support the presence of disulfide units within the polymer. The solid-state (13)C NMR (99 % (13)C-labelled) spectrum is dominated by two singlets of equal intensity at approximately 187 and 184 ppm with low intensity peaks in the range 152-172 ppm, in approximately the same range as both 1,2,4-thiadiazoles and 1,2,4-dithiazoles. The solid-state (15)N NMR (99 % (15)N labelled) spectrum displays two major peaks of similar intensity at 236.9 and 197.2 ppm, which are clearly very different environments to those observed in bis(3-bromo-1,2,4-thiadiazol-5-yl) disulfide, but similar to 1,2,4-dithiazoles. The X-ray structures of seven C-S-N systems are reported. Preliminary studies on (SeCN)(x) suggest that literature references to this polymer may be in error with the red solid actually being red selenium. 相似文献
99.
Bowman A Allix M Pelloquin D Rosseinsky MJ 《Journal of the American Chemical Society》2006,128(39):12606-12607
The n = 3 Ruddlesden-Popper phase Sr3LaFe1.5Co1.5O10+/-delta is capable of sustaining O contents as low as O7.5 with a mean metal oxidation state of +2 and three coordination at the central site in the trilayer of originally octahedral transition metal sites. The shortening of the axial bonds to the flanking octahedral layers stabilizes the low oxidation state and consequent unusual low coordination number of the Fe2+ and Co2+ cations within the extended structure. 相似文献
100.
A number of new, layered nitride mixed halides have been synthesised in the quaternary phase systems Sr-N-Cl-Br and Sr-N-Br-I. The variation in structure with composition has been investigated by powder X-ray and powder neutron diffraction techniques and the structure of strontium nitride iodide, Sr2NI, has been determined for the first time (rhombohedral space group R-3m, , , Z=3). A continuous solid solution exists between Sr2NCl and Sr2NBr with intermediate compounds adopting the same anti-α-NaFeO2 structure (rhombohedral space group R-3m) as the ternary end members. A similar smooth and linear relationship between structure and composition is seen from Sr2NBr to Sr2NI and hence cubic close packing of metal-nitrogen layers is adopted regardless of halide, X (X′). While nitride and halide anions occupy distinct crystallographic sites, there is no ordering of the halides in the quaternary materials irrespective of stoichiometry or temperature (between 3 and 673 K). 相似文献