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The effect of external forces on the initial dissociation of RDX (1,3,5‐trinitro‐1,3,5‐triazine): A mechanochemical study 下载免费PDF全文
Guido Todde Sanjiv K. Jha Gopinath Subramanian 《International journal of quantum chemistry》2017,117(20)
Experimental and theoretical studies have proposed different initiation reactions for the decomposition of hexahydro‐1,3,5‐trinitro‐1,3,5‐triazine (RDX). Three primary reactions are considered to start RDX decomposition: homolytic N? N bond fission, HONO elimination, and concerted fission of C? N bonds. The focus of this article is to study the effect of external forces on the energy barrier and reaction energies of all three mechanisms. We used the Nudged Elastic Band method along with ab initio Density Functional Theory within the framework of a generalized force‐modified potential energy surface (G‐FMPES) to calculate the minimum energy paths at different compressive (corresponding to pressure between approximately 6 and 294 MPa) and expansive force values (between 10 and 264 pN). For all three reactions, the application of an expansive force increases the exothermicity and lowers the energy barriers to different extents, while a compressive force decreases the exothermicity and raises the energy barrier to different extents. 相似文献
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Archana Sivasubramaniyan Ranganathan Raja Dinesh Murugan Arul Ponnusamy Ponnuswamy Alagusundaram Kalaiselvi Patchaiah Chellammal Subbiah Subramanian Gopalan 《Research on Chemical Intermediates》2017,43(4):2471-2490
Research on Chemical Intermediates - A library of pyrazolinyltriazole hybrids (3a–l, 4a–l) was synthesized via azide–alkyne dipolar (Huisgen) cycloaddition of azidoacetyl... 相似文献
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The thermodynamics of the complexing between hexavalent U and 1-phenyl-3-methyl-4-benzoylpyrazolone-5 (PMBP) have been studied in 70 vol% aqueous—dioxane medium at 25 and 35±0.1°C following the Bjerrum—Calvin pH titration technique, as applied by Van Uitert and Haas. The ligand is mono-protonic. The refinement of results of formation constants has been accomplished by the method of least squares treatment after an algebraic transformation. The formation of 1:1, 1:2 and 1:3 complexes has been observed, the order of stability being log K1 > log K2 > log K3. The stability invariably increases with an increase in temperature both in aqueous as well as aqueous dioxane media. The changes in ΔG0, ΔH0 and ΔS0 at 25 and 35°C for the overall equilibrium constants have also been evaluated. Uranyl complexes of PMBP are entropy stabilized, the values of enthalpy changes being positive. Other factors which affect chelate stability are briefly discussed. 相似文献
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Novel ternary composite photocatalysts have been successfully prepared by TiO₂ nanofibers, reduced graphene oxide, and CdS nanoparticles (TiO₂/rGO/CdS) by using electrospinning technique with easy chemical methods. The structures and their properties are examined by X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), and field-emission scanning electron microscope (FESEM). The structural characterization of the composite reveals that pure TiO₂ NFs and CdS NPs crystalline very well and the reduced graphene oxide is tightly composed with TiO₂ NFs and CdS Nps. The photodegradation of methyl orange (MO) under UV light illumination is significantly enhanced compared with that of bare materials. This ternary composite degrades methyl orange within 75 min. The enhanced photocatalytic degradation performance resulted from effective separation of e–h pairs with rGO sheets and also contributed for high rate degradation efficiency. This novel ternary composite has a potential application of wastewater purification and utilization for energy conversions. 相似文献
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Karthikraja Esackraj Dr. Naga Venkateswara Rao Nulakani Dr. Venkata Surya Kumar Choutipalli Dr. Chandra Chowdhury Dr. Palanichamy Murugan Dr. V. G. Vaidyanathan Prof. Venkatesan Subramanian 《Chemphyschem》2023,24(11):e202300035
Generally, graphynes have been generated by the insertion of acetylenic content (−C≡C−) in the graphene network in different ratios. Also, several aesthetically pleasing architectures of two-dimensional (2D) flatlands have been reported with the incorporation of acetylenic linkers between the heteroatomic constituents. Prompted by the experimental realization of boron phosphide, which has provided new insights on the boron-pnictogen family, we have modelled novel forms of acetylene-mediated borophosphene nanosheets by joining the orthorhombic borophosphene stripes with different widths and with different atomic constituents using acetylenic linkers. Structural stabilities and properties of these novel forms have been assessed using first-principles calculations. Investigation of electronic band structure elucidates that all the novel forms show the linear band crossing closer to the Fermi level at Dirac point with distorted Dirac cones. The linearity in the hole and electronic bands impose the high Fermi velocity to the charge carriers close to that of graphene. Finally, we have also unravelled the propitious features of acetylene-mediated borophosphene nanosheets as anodes in Li-ion batteries. 相似文献
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Priv.-Doz. Dr. K. -P. Kistner Dr. R. Subramanian 《Mathematical Methods of Operations Research》1974,18(3):117-129
Zusammenfassung Es wird die Zuverlässigkeit eines Systems mit mehreren redundanten Einheiten untersucht, bei dem nicht nur die tätige Einheit, sondern auch die Reserveeinheiten ausfallen und bei dem gestörte Einheiten repariert werden können. Es wird vorausgesetzt, daß die Reparaturzeiten und die Lebensdauern der Reserveeinheiten exponentialverteilt sind, während die Betriebsdauern der tätigen Einheiten, unabhängig von ihrem Alter beim Einsatz, beliebig verteilt sind.Unter diesen Voraussetzungen werden die mittlere Zeit bis zum Ausfall des Systems und die langfristige Verfügbarkeit des Systems explizit für den Fall dreier Einheiten bestimmt.Am Beispiel doppel-exponentialverteilter Betriebsdauern werden die Abhängigkeit dieser Größen von der Reparaturgeschwindigkeit untersucht und die optimale Reparaturrate bestimmt.
Diese Arbeit wurde durch den Sonderforschungsbereich 21 — ökonometrie und Unternehmensforschung — und ein Stipendium der Alexander-von-Humboldt-Stiftung gefördert. 相似文献
Summary We consider the reliability of a repairable system with several stand-by redundant units, where not only the working unit but also the spares are subject to failure. We assume, that repair-times and life-times of spares are exponentially distributed, whereas the time to failure of a working unit is — independent of its age at the time of switch-on — arbitrarily distributed.Using these assumptions, we derive the expected time to system-failure and the steady-state availability explicitely for the case of three redundant units. The example of double-exponentially distributed working-times is used to examine the dependancy of these characteristics on repair-times, and to calculate the optimal repair-rate.
Diese Arbeit wurde durch den Sonderforschungsbereich 21 — ökonometrie und Unternehmensforschung — und ein Stipendium der Alexander-von-Humboldt-Stiftung gefördert. 相似文献
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