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《Annales de l'Institut Henri Poincaré (C) Analyse Non Linéaire》2021,38(5):1337-1371
In this paper we consider minimizers of the functional where is a bounded open set and where are the first k eigenvalues on Ω of an operator in divergence form with Dirichlet boundary condition and with Hölder continuous coefficients. We prove that the optimal sets have finite perimeter and that their free boundary is composed of a regular part, which is locally the graph of a -regular function, and a singular part, which is empty if , discrete if and of Hausdorff dimension at most if , for some . 相似文献
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文章首先将史瓦西黑洞场中自由下落质点的固有时(诺维科夫坐标时)公式,由自然单位制化成了国际单位制中的形式.然后,根据牛顿第二定律和万有引力定律,推导出了自由下落质点经历的绝对时间公式,进而证明了广义相对论中自由落体经历的固有时,恰好等于牛顿力学给出的绝对时间.最后,对自由下落质点在黑洞内外经历的时间进行了特例计算. 相似文献
4.
Benni Du 《Molecular physics》2020,118(2)
Kinetics and mechanism of the gas-phase reaction of CH3C(O)OCH(CH3)CH2OCH3 (MPA) with OH radicals in the presence of O2 and NO have been investigated theoretically by performing a high and reliable level of theory, viz., CCSD(T)/6-311?+?G(d,p)//BH&HLYP/6-311++G(d,p)?+?0.9335×ZPE. The calculations predict that the H-abstraction from the ?CH2?O? position of MPA is the most facile channel, which leads to the formation of the corresponding alkoxy radicals CH3C(O)OCH(CH3)C(O ?)HOCH3 under atmospheric conditions. This activated radicals CH3C(O)OCH(CH3)C(O ?)HOCH3 will undergo further rearrangement, fragmentation and oxidative reactions and predominantly leads to the formation of various products (methyl formate HC(O)OCH3 and acetic anhydride CH3C(O)OC(O)CH3). In the presence of water, acetic anhydride can convert into acetic acid CH3C(O)OH via the hydrolysis reaction. The calculated total rate constants over the temperature range 263–372?K are used to derive a negative activation energy (Ea= ?5.88 kJ/mol) and an pre-exponential factor (A?=?1.78×10?12 cm3 molecule?1 s?1). The obtained Arrhenius parameters presented here are in strong agreement with the experimental values. Moreover, the temperature dependence of the total rate constant over a temperature range of 263?1000?K can be described by k?=?5.60 × 10?14×(T/298?K)3.4×exp(1725.7?K/T) cm3 molecule?1 s?1. 相似文献
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New Phenomena in Organometallic‐Mediated Radical Polymerization (OMRP) and Perspectives for Control of Less Active Monomers 下载免费PDF全文
Prof. Dr. Rinaldo Poli 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(19):6988-7001
The impact of reversible bond formation between a growing radical chain and a metal complex (organometallic‐mediated radical polymerization (OMRP) equilibrium) to generate an organometallic intermediate/dormant species is analyzed with emphasis on the interplay between this and other one‐electron processes involving the metal complex, which include halogen transfer in atom transfer radical polymerization (ATRP), hydrogen‐atom transfer in catalytic chain transfer (CCT), and catalytic radical termination (CRT). The challenges facing the controlled polymerization of “less active monomers” (LAMs) are outlined and, after reviewing the recent achievements of OMRP in this area, the perspectives of this technique are analyzed. 相似文献
7.
Leonor Contreras Ignacio Villarroel Camila Torres Roberto Rozas 《Molecules (Basel, Switzerland)》2021,26(6)
Doxorubicin (DOX), a recognized anticancer drug, forms stable associations with carbon nanotubes (CNTs). CNTs when properly functionalized have the ability to anchor directly in cancerous tumors where the release of the drug occurs thanks to the tumor slightly acidic pH. Herein, we study the armchair and zigzag CNTs with Stone–Wales (SW) defects to rank their ability to encapsulate DOX by determining the DOX-CNT binding free energies using the MM/PBSA and MM/GBSA methods implemented in AMBER16. We investigate also the chiral CNTs with haeckelite defects. Each haeckelite defect consists of a pair of square and octagonal rings. The armchair and zigzag CNT with SW defects and chiral nanotubes with haeckelite defects predict DOX-CNT interactions that depend on the length of the nanotube, the number of present defects and nitrogen doping. Chiral nanotubes having two haeckelite defects reveal a clear dependence on the nitrogen content with DOX-CNT interaction forces decreasing in the order 0N > 4N > 8N. These results contribute to a further understanding of drug-nanotube interactions and to the design of new drug delivery systems based on CNTs. 相似文献
8.
Physical aging in amorphous poly(ethylene furanoate): Enthalpic recovery,density, and oxygen transport considerations 下载免费PDF全文
Steven K. Burgess Christopher R. Mubarak Robert M. Kriegel William J. Koros 《Journal of Polymer Science.Polymer Physics》2015,53(6):389-399
The current work utilizes three separate techniques to study the physical aging process in amorphous poly(ethylene furanoate) (PEF), which is a recently introduced engineering thermoplastic with enhanced properties compared to petroleum‐sourced poly(ethylene terephthalate). Differential scanning calorimetry aging experiments were conducted at multiple aging temperatures and times, and the resultant enthalpic recovery values compared to the theoretical maximum enthalpy loss evaluated from calculations involving extrapolation of the equilibrium liquid line. Density measurements reveal densification of the matrix for the aged versus unaged samples, and provide an estimate for the reduction in free volume for the aged samples. Complementary oxygen permeation and pressure‐decay sorption experiments provide independent verification of the free volume reduction mechanism for physical aging in glassy polymers. The current work provides the first detailed aging study for PEF. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 389–399 相似文献
9.
Roberto Morales-Cerrada Dr. Christophe Fliedel Dr. Jean-Claude Daran Dr. Florence Gayet Dr. Vincent Ladmiral Dr. Bruno Améduri Prof. Rinaldo Poli 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(1):296-308
Thermal decarbonylation of the acyl compounds [Mn(CO)5(CORF)] (RF=CF3, CHF2, CH2CF3, CF2CH3) yielded the corresponding alkyl derivatives [Mn(CO)5(RF)], some of which have not been previously reported. The compounds were fully characterized by analytical and spectroscopic methods and by several single-crystal X-ray diffraction studies. The solution-phase IR characterization in the CO stretching region, with the assistance of DFT calculations, has allowed the assignment of several weak bands to vibrations of the [Mn(12CO)4(eq-13CO)(RF)] and [Mn(12CO)4(ax-13CO)(RF)] isotopomers and a ranking of the RF donor power in the order CF3<CHF2<CH2CF3≈CF2CH3. The homolytic Mn−RF bond cleavage in [Mn(CO)5(RF)] at various temperatures under saturation conditions with trapping of the generated RF radicals by excess tris(trimethylsilyl)silane yielded activation parameters ΔH≠ and ΔS≠ that are believed to represent close estimates of the homolytic bond dissociation thermodynamic parameters. These values are in close agreement with those calculated in a recent DFT study (J. Organomet. Chem. 2018 , 864, 12–18). The ability of these complexes to undergo homolytic Mn−RF bond cleavage was further demonstrated by the observation that [Mn(CO)5(CF3)] (the compound with the strongest Mn−RF bond) initiated the radical polymerization of vinylidene fluoride (CH2=CF2) to produce poly(vinylidene fluoride) in good yields by either thermal (100 °C) or photochemical (UV or visible light) activation. 相似文献
10.
Greg Orosi 《商业与工业应用随机模型》2015,31(4):515-527
In this work, we suggest a novel quadratic programming‐based algorithm to generate an arbitrage‐free call option surface. The empirical performance of the proposed method is evaluated using S&P 500 Index call options. Our results indicate that the proposed method provides a more precise fit to observed option prices than other alternative methodologies. Copyright © 2014 John Wiley & Sons, Ltd. 相似文献