Blow-up and stability of semilinear PDEs with Gamma generators
上半空间高次分数阶Laplace方程解的不存在性

上半空间高次分数阶Laplace方程解的不存在性李冬艳;陈文雄【摘要】Nonexistence of positive solutions for equations involving higher order fractional Laplacians with Navier conditions in an upper-half space is considered.Narrow region principle of higher-order fractional Laplacian equations is established by using iterative method.And then with method of moving planes,nonexistence of positive solutions for equations involving higher-order fractional Laplacians with Navier conditions is proved.%研究上半空间中带Navier条件的高次分数阶Laplace方程正解的不存在性.借助迭代法,建立高次分数阶方程的狭窄区域原理;然后结合移动平面法,证明具有Navier条件的高次分数阶方程正解的不存在性.【期刊名称】《纺织高校基础科学学报》【年(卷),期】2017(030)001【总页数】5页(P18-22)【关键词】高次分数阶Laplace方程;Navier条件;狭窄区域极值原理;解不存在性【作者】李冬艳;陈文雄【作者单位】西安工程大学理学院,陕西西安710048;叶史瓦大学,美国纽约10033【正文语种】中文【中图分类】O175分数阶Laplace算子是一个非局部拟微分算子,定义为其中α为0与2之间的任意实数,且近年来,分数阶Laplace方程问题倍受关注,它在描述一系列物理现象中有着重要的作用,如不规则扩散现象[1-2]、气象学中的准地转流[3-4]、湍流模型、分子动力学以及相对量子力学[5-6]等,甚至在金融和概率方面[7-8]也有着广泛的应用.在基础研究方面,对测度椭圆问题、非一致椭圆问题[9]以及势梯度问题[10]也不可或缺.为克服分数阶Laplace的非局部性,Caffarelli-Silvestre引进了延拓法[11],将非局部问题转化成更高维Rn×[0,∞)中的局部问题,从而成为研究带有分数阶Laplace算子方程的有力工具.后来,Chen等[12]提出了一种直接对分数阶方程进行的移动平面法,这种方法对有界区域及无界区域均有效,成为证明分数阶非线性方程正解的对称性、单调性及不存在性的有力工具.在式(1)的基础上,定义如下高次的分数阶Laplace算子.当0<α<2时,式(1)可以等价的写为其中Sr(x)是以x为中心,r为半径的球面.当r充分小且y∈Sr(x)时,因为,做Taylor 展开可得由对称性得从而有显然,该积分当α<2时收敛,当α>2时发散.因此,当2<α<4时,为使积分收敛,定义高次的分数阶Laplace算子为当,类似地,由Taylor展开及对称性,则有该积分当α<4时收敛,当α>4时发散.本文考虑上半空间{x=(x1,x2,…xn)|xn≥0}中具有Navier条件的高次分数阶非线性方程其中,,0<α<2.移动平面法已在证明方程正解对称性[13],不存在性[14]及解的先验估计[15]等方面发挥过重要作用.但目前为止,移动平面法还不能被直接应用到高次分数阶方程上.因此,本文先将高次分数阶方程化成低次方程组,然后再应用移动平面法.为此,需要以下两个引理,其在后续证明中起着重要作用.引理1 设H={x∈Rn|0<xn<λ,λ∈R}是Σ内的一个无界区域.设,且U,V在上下半连续.若其中c(x)<0,且当|x|充分大时,c(x)则存在常数R0>0,使得若那么引理2[16] 设Ω⊂∑λ={x∈Rn|xn<λ}是有界狭窄区域,不失一般性,假设Ω包含在狭窄区域{x∈Rn|λ-l<xn<λ}中,l充分小.考虑方程组其中ci(x)≤0,i=1,2有界,在中下半连续.则当l充分小时,有对无界区域Ω,若U(x),V(x)→0, |x|→∞,式(3)仍成立.并且,若存在一点x0∈Ω,使得U(x0)=0或V(x0)=0,则基于狭窄区域原理,可以沿xn方向做移动平面,证明正解关于xn单调,从而得到以下结论.定理1 设(m>0)是方程(2)的正解,f(t)满足以下条件:(Ⅰ) 关于t单调增且Lipschitz连续;(Ⅱ).则u(x)≡0.为方便证明,采用以下记号.设Tλ={x∈Rn|xn=λ},Σλ={x∈Rn|xn<λ},且xλ={(x1,x2,…,2λ-xn)|x=(x1,x2,…,xn)∈Rn}是点x关于平面Tλ的对称点.定理1的证明令-Δu=v,则方程(2)可以写成如下两个方程:及设uλ(x)=u(xλ), Uλ(x)=uλ(x)-u(x), Vλ(x)=vλ(x)-v(x). 则有Step 1 证明当λ充分小时,有因为取引理2中的Ω为,则当λ充分小时,Ω为狭窄区域,且当λ固定时,当|x|→+∞时,|xλ|→+∞.从而由可知,u(x)→0, |x|→∞且uλ(x)→0, |x|→∞.所以当x∈Σλ时, 同理,可证则由引理2可得其中,c1(x)=-1, c2(x)=c(x).由f(x)为Lipschitz连续性,c2(x)是有界的,而f(x)的单增性保证了c2(x)≤0.Step 2 由式(4),从xn=0附近开始移动平面Tλ,只要Uλ(x)≥0, Vλ(x)≥0成立,则一直沿xn轴移动平面.定义接下来证明利用反证法.如若λ0<+∞,则必有由式(5)可知,平面xn=2λ0是边界关于平面Tλ0的对称平面.由边界条件及uλ0关于Tλ0的对称性知,在xn=2λ0上有u(x)=0,这与u(x)>0矛盾.从而λ0=+∞. 即方程正解u(x)关于变量xn单调增加.这与在无穷远处矛盾,从而方程无正解.现在证明式(5)成立.假设式(5)不成立,则由强极值原理,有则可以继续沿xn方向移动平面Tλ0,说明存在一个ε>0,使得∀λ∈[λ0,λ0+ε),有成立.这与λ0的定义矛盾,从而式(5)成立.接下来证明式(7)成立.假设式(7)不成立,即存在点,使得则从而存在一点,使得由条件(Ⅰ)、(Ⅱ)知,因此,c(x)满足引理1中的条件,从而存在R0,使得固定R0,则对任意小的δ>0,由式(6)知,存在常数C,使得即但由引理2知,在狭窄区域(Σλ\Σλ0-δ)∩BR0(0)内,矛盾,即式(7)成立.定理1证毕.E-mail:************LI Dongyan,CHEN Wenxiong.Nonexistence of positive solutions for higher order fractional Laplacians in an upper-half space[J].Basic Sciences Journal of Textile Universities,2017,30(1):18-22.【相关文献】[1] METZLER R,KLAFTER J.The random walk′s guide to anomalous diffusion:A fractional dynamics approach[J].Physics Reports-Review Section of Physics Letters,2000,339(1):1-77.[2] MELLET A,MISCHLER S,MOUHOT C.Fractional diffusion limit for collisional kinetic equations[J].Archive of Rational Mechanics and Analysis,2011,199(2):493-525.[3] CAFFARELLI L,VASSEUR A.Drift diffusion equations with fractional diffusion and the quasi-geostrophic equation[J].Annals of Mathematics,2010,171(3):1903-1930.[4] CORDOBA D.Nonexistence of simple hyperbolic blow-up for the quasi-geostrophic equation[J].Annals of Mathematics,1998,148(3):1135-1152.[5] BOUCHARD J P,GEORGES A.Anomalous diffusion in disordered media,statistical mechanics,models and physical applications[J].Physics Reports,1990,195(4/5):127-293. [6] TARASOV V,ZASLASVKY G.Fractional dynamics of systems with long-range interaction[J].Communications in Nonlinear Science & NumericalSimulation,2006,11(8):885-889.[7] APPLEBAUM D.L′evy processes and stochastic calculus[M].2ndedition.Cambridge:Cambridge University Press,2009.[8] CONT R,TANKOV P.Financial modelling with jump processes[M].Boca Raton:Chapman & Hall/CRC Financial Mathematics Series,2004.[9] ESPOSITO L,LEONETTI F,MINGIONE G.Sharp regularity for functionals with (p,q) growth[J].Journal of Differential Equations,2004,204(1):5-55.[10] MINGIONE G.Gradient potential estimates[J].Journal of the European Mathmatical Society,2011,13(2):459-486.[11] CAFFARELLI L,SILVESTRE L.An extension problem related to the fractional Laplacian[J].Communications in Partial Differential Equations,2007,32(8):1245-1260. [12] CHEN Wenxiong,LI Congming,LI Yan.A direct method of moving planes for thefractional Laplacian[J].Advances in Mathematics,2017,308:404-437.[13] ZHANG Lizhi.Symmetry of solutions to semilinear equations involving the fractional Laplacian[J].Communication on Pure and Applied Analysis,2015,14(6):2393-2409. [14] CHEN Wenxiong,FANG Yanqin,YANG Ray.Semilinear equations involving the fractional Laplacian on a half space[J].Advances in Mathematics,2015,274(8):167-198. [15] CHEN Wenxiong,LI Congming.A priori estimates for prescribing scalar curvature equations[J].Annals of Mathematics,1997,145(3):547-564.[16] ZHUO Ran,LI Yan.A Liouville theorem for the higher order fractionalLaplacian[J].arXiv:1609.04105[math.AP].。
One-step strategy to three-dimensional graphene_

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Huanwen Wang, Huan Yi, Xiao Chen and Xuefeng Wang*
A facile one-step strategy has been developed to prepare 3D graphene/VO2 nanobelt composite hydrogels, which can be readily scaled-up for mass production by using commercial V2O5 and graphene oxide as precursors. During the formation of the graphene/VO2 architecture, 1D VO2 nanobelts and 2D flexible graphene sheets are self-assembled to form interconnected porous microstructures through hydrogen bonding, which facilitates charge and ion transport in the electrode. Due to the hierarchical network framework and the pseudocapacitance contribution from VO2 nanobelts, the hybrid electrode demonstrates excellent capacitive performances. In the two-electrode configuration, the graphene/VO2 nanobelt composite hydrogel exhibits a specific capacitance of 426 F gÀ1 at 1 A gÀ1 in the potential range of À0.6 to 0.6 V, which greatly surpasses that of each individual counterpart (191 F gÀ1 and 243 F gÀ1 at 1 A gÀ1 for VO2 nanobelt and graphene hydrogel, respectively). The hybrid electrode also shows an improved rate capability and cycling stability, which is indicative of a positive synergistic effect of VO2 and graphene on the improvement of electrochemical performance. These findings reveal the importance and great potential of graphene composite hydrogels in the development of energy storage devices with high power and energy densities.
用初中英语简要介绍双缝实验

用初中英语简要介绍双缝实验The Double-Slit ExperimentThe double-slit experiment is a fundamental experiment in quantum mechanics that demonstrates the wave-particle duality of light and other quantum particles. It was first performed by the English physicist Thomas Young in 1801, and it has since become one of the most famous experiments in the history of science.The basic setup of the double-slit experiment is as follows. A source of light, such as a laser or a monochromatic light source, is directed towards a barrier that has two narrow slits cut in it. The light passing through the slits is then projected onto a screen or a detector. When the light passes through the two slits, it creates an interference pattern on the screen, with alternating bright and dark regions.This interference pattern is a clear demonstration of the wave-like nature of light. If light were simply a stream of particles, one would expect to see two separate bright spots on the screen, corresponding to the two slits. However, the interference pattern shows that the light is behaving like a wave, with the waves from the two slits interfering with each other.The double-slit experiment can also be performed with other quantum particles, such as electrons or atoms. When these particles are directed towards the double slit, they also exhibit an interference pattern, indicating that they too have a wave-like nature.The wave-particle duality of quantum particles is a fundamental concept in quantum mechanics. It means that particles can exhibit both wave-like and particle-like properties, depending on the experiment being performed. This is a departure from the classical view of the world, where objects were either waves or particles, but not both.The double-slit experiment has been used to demonstrate the wave-particle duality of various quantum particles, including electrons, neutrons, atoms, and even large molecules. In each case, the interference pattern observed on the screen is a clear indication of the wave-like nature of the particles.One of the most interesting aspects of the double-slit experiment is the role of the observer. When the experiment is set up to detect which slit the particle goes through, the interference pattern disappears, and the particles behave like classical particles. This suggests that the act of measurement or observation can affect the behavior of quantum particles.This is a concept known as the "observer effect" in quantum mechanics, and it has profound implications for our understanding of the nature of reality. It suggests that the very act of observing or measuring a quantum system can alter its behavior, and that the observer is not a passive participant in the experiment.The double-slit experiment has also been used to explore the concept of quantum entanglement, which is another fundamental concept in quantum mechanics. Quantum entanglement occurs when two or more quantum particles become "entangled" with each other, such that the state of one particle is dependent on the state of the other.In the double-slit experiment, the interference pattern can be used to demonstrate the phenomenon of quantum entanglement. For example, if two particles are entangled and then directed towards the double slit, the interference pattern observed on the screen will depend on the state of the entangled particles.Overall, the double-slit experiment is a powerful and versatile tool for exploring the fundamental nature of reality at the quantum level. It has been used to demonstrate the wave-particle duality of light and other quantum particles, the observer effect, and the phenomenon of quantum entanglement. As such, it remains one ofthe most important and influential experiments in the history of science.。
通常的化合物结晶是通过降温实现,但这篇钙钛矿的结晶是通过升温实现的,而且速度超快,还是单晶-2015-NC

of Physical Sciences and Engineering, Solar and Photovoltaics Engineering Research Center, King Abdullah University of Science and Technology (KAUST), Thuwal 23955-6900, Kingdom of Saudi Arabia. 2 Department of Chemistry, Faculty of Science, Mansoura University, Mansoura 35516, Egypt. 3 Mathematical Institute, University of Oxford, Woodstock Road, Oxford OX2 6GG, UK. 4 Materials Science and Engineering, King Abdullah University of Science and Technology (KAUST), Thuwal 23955-6900, Kingdom of Saudi Arabia. 5 Imaging and Characterization Lab, King Abdullah University of Science and Technology (KAUST), Thuwal 23955-6900, Kingdom of Saudi Arabia. * These authors contributed equally to this work. Correspondence and requests for materials should be addressed to O.M.B. (email: osman.bakr@.sa).
光谱法研究药物小分子与蛋白质大分子的相互作用的英文

Spectroscopic Study of the Interaction between Small Molecules and Large Proteins1. IntroductionThe study of drug-protein interactions is of great importance in drug discovery and development. Understanding how small molecules interact with proteins at the molecular level is crucial for the design of new and more effective drugs. Spectroscopic techniques have proven to be valuable tools in the investigation of these interactions, providing det本人led information about the binding affinity, mode of binding, and structural changes that occur upon binding.2. Spectroscopic Techniques2.1. Fluorescence SpectroscopyFluorescence spectroscopy is widely used in the study of drug-protein interactions due to its high sensitivity and selectivity. By monitoring the changes in the fluorescence emission of either the drug or the protein upon binding, valuable information about the binding affinity and the binding site can be obt本人ned. Additionally, fluorescence quenching studies can provide insights into the proximity and accessibility of specific amino acid residues in the protein's binding site.2.2. UV-Visible SpectroscopyUV-Visible spectroscopy is another powerful tool for the investigation of drug-protein interactions. This technique can be used to monitor changes in the absorption spectra of either the drug or the protein upon binding, providing information about the binding affinity and the stoichiometry of the interaction. Moreover, UV-Visible spectroscopy can be used to study the conformational changes that occur in the protein upon binding to the drug.2.3. Circular Dichroism SpectroscopyCircular dichroism spectroscopy is widely used to investigate the secondary structure of proteins and to monitor conformational changes upon ligand binding. By analyzing the changes in the CD spectra of the protein in the presence of the drug, valuable information about the structural changes induced by the binding can be obt本人ned.2.4. Nuclear Magnetic Resonance SpectroscopyNMR spectroscopy is a powerful technique for the investigation of drug-protein interactions at the atomic level. By analyzing the chemical shifts and the NOE signals of the protein in thepresence of the drug, det本人led information about the binding site and the mode of binding can be obt本人ned. Additionally, NMR can provide insights into the dynamics of the protein upon binding to the drug.3. Applications3.1. Drug DiscoverySpectroscopic studies of drug-protein interactions play a crucial role in drug discovery, providing valuable information about the binding affinity, selectivity, and mode of action of potential drug candidates. By understanding how small molecules interact with their target proteins, researchers can design more potent and specific drugs with fewer side effects.3.2. Protein EngineeringSpectroscopic techniques can also be used to study the effects of mutations and modifications on the binding affinity and specificity of proteins. By analyzing the binding of small molecules to wild-type and mutant proteins, valuable insights into the structure-function relationship of proteins can be obt本人ned.3.3. Biophysical StudiesSpectroscopic studies of drug-protein interactions are also valuable for the characterization of protein-ligandplexes, providing insights into the thermodynamics and kinetics of the binding process. Additionally, these studies can be used to investigate the effects of environmental factors, such as pH, temperature, and ionic strength, on the stability and binding affinity of theplexes.4. Challenges and Future DirectionsWhile spectroscopic techniques have greatly contributed to our understanding of drug-protein interactions, there are still challenges that need to be addressed. For instance, the study of membrane proteins and protein-protein interactions using spectroscopic techniques rem本人ns challenging due to theplexity and heterogeneity of these systems. Additionally, the development of new spectroscopic methods and the integration of spectroscopy with other biophysical andputational approaches will further advance our understanding of drug-protein interactions.In conclusion, spectroscopic studies of drug-protein interactions have greatly contributed to our understanding of how small molecules interact with proteins at the molecular level. Byproviding det本人led information about the binding affinity, mode of binding, and structural changes that occur upon binding, spectroscopic techniques have be valuable tools in drug discovery, protein engineering, and biophysical studies. As technology continues to advance, spectroscopy will play an increasingly important role in the study of drug-protein interactions, leading to the development of more effective and targeted therapeutics.。
全氧烧嘴-速焰英国

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Industrial Burners Handbook
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21.2.1.1 High Flame Temperature and Heat Transfer High adiabatic flame temperature and high heat release rate and transfer are the main benefits for which traditional applications of oxy-fuel burners were developed. Welding with an oxy-acetylene flame, flame polishing of glass surfaces, and oxygen cutting of steel plates are some of examples of applications that take advantage of these oxy-fuel flame characteristics. 21.2.1.2 Fuel Savings The use of oxygen in a heating process eliminates the nitrogen introduced with combustion air from the process and hence eliminates the energy required to heat the nitrogen from inlet temperature to outlet temperature. For high-temperature processes (>2200°F or 1200°C) with no heat recovery, fuel savings when using oxygen can exceed 50%. As heat recovery is employed with the air combustion system, the savings achievable when switching to oxy-fuel combustion are reduced. A simple heat and mass balance on the furnace under each operating condition can provide accurate
单分子综述-NATURE NANOTECHNOLOGY-Single-molecule junctions beyond electronic transport-2013
Stimulated by the initial proposal that molecules could be used as the functional building blocks in electronic devices 1, researchers around the world have been probing transport phenomena at the single-molecule level both experimentally and theoretically 2–11. Recent experimental advances include the demonstration of conductance switching 12–16, rectification 17–21, and illustrations on how quantum interference effects 22–26 play a critical role in the electronic properties of single metal–molecule–metal junctions. The focus of these experiments has been to both provide a fundamental understanding of transport phenomena in nanoscale devices as well as to demonstrate the engineering of functionality from rational chemical design in single-molecule junctions. Although so far there are no ‘molecular electronics’ devices manufactured commercially, basic research in this area has advanced significantly. Specifically, the drive to create functional molecular devices has pushed the frontiers of both measurement capabilities and our fundamental understanding of varied physi-cal phenomena at the single-molecule level, including mechan-ics, thermoelectrics, optoelectronics and spintronics in addition to electronic transport characterizations. Metal–molecule–metal junctions thus represent a powerful template for understanding and controlling these physical and chemical properties at the atomic- and molecular-length scales. I n this realm, molecular devices have atomically defined precision that is beyond what is achievable at present with quantum dots. Combined with the vast toolkit afforded by rational molecular design 27, these techniques hold a significant promise towards the development of actual devices that can transduce a variety of physical stimuli, beyond their proposed utility as electronic elements 28.n this Review we discuss recent measurements of physi-cal properties of single metal–molecule–metal junctions that go beyond electronic transport characterizations (Fig. 1). We present insights into experimental investigations of single-molecule junc-tions under different stimuli: mechanical force, optical illumina-tion and thermal gradients. We then review recent progress in spin- and quantum interference-based phenomena in molecular devices. I n what follows, we discuss the emerging experimentalSingle-molecule junctions beyond electronic transportSriharsha V. Aradhya and Latha Venkataraman*The id ea of using ind ivid ual molecules as active electronic components provid ed the impetus to d evelop a variety of experimental platforms to probe their electronic transport properties. Among these, single-molecule junctions in a metal–molecule–metal motif have contributed significantly to our fundamental understanding of the principles required to realize molecular-scale electronic components from resistive wires to reversible switches. The success of these techniques and the growing interest of other disciplines in single-molecule-level characterization are prompting new approaches to investigate metal–molecule–metal junctions with multiple probes. Going beyond electronic transport characterization, these new studies are highlighting both the fundamental and applied aspects of mechanical, optical and thermoelectric properties at the atomic and molecular scales. Furthermore, experimental demonstrations of quantum interference and manipulation of electronic and nuclear spins in single-molecule circuits are heralding new device concepts with no classical analogues. In this Review, we present the emerging methods being used to interrogate multiple properties in single molecule-based devices, detail how these measurements have advanced our understanding of the structure–function relationships in molecular junctions, and discuss the potential for future research and applications.methods, focusing on the scientific significance of investigations enabled by these methods, and their potential for future scientific and technological progress. The details and comparisons of the dif-ferent experimental platforms used for electronic transport char-acterization of single-molecule junctions can be found in ref. 29. Together, these varied investigations underscore the importance of single-molecule junctions in current and future research aimed at understanding and controlling a variety of physical interactions at the atomic- and molecular-length scale.Structure–function correlations using mechanicsMeasurements of electronic properties of nanoscale and molecu-lar junctions do not, in general, provide direct structural informa-tion about the junction. Direct imaging with atomic resolution as demonstrated by Ohnishi et al.30 for monoatomic Au wires can be used to correlate structure with electronic properties, however this has not proved feasible for investigating metal–molecule–metal junctions in which carbon-based organic molecules are used. Simultaneous mechanical and electronic measurements provide an alternate method to address questions relating to the struc-ture of atomic-size junctions 31. Specifically, the measurements of forces across single metal–molecule–metal junctions and of metal point contacts provide independent mechanical information, which can be used to: (1) relate junction structure to conduct-ance, (2) quantify bonding at the molecular scale, and (3) provide a mechanical ‘knob’ that can be used to control transport through nanoscale devices. The first simultaneous measurements of force and conductance in nanoscale junctions were carried out for Au point contacts by Rubio et al.32, where it was shown that the force data was unambiguously correlated to the quantized changes in conductance. Using a conducting atomic force microscope (AFM) set-up, Tao and coworkers 33 demonstrated simultaneous force and conductance measurements on Au metal–molecule–metal junc-tions; these experiments were performed at room temperature in a solution of molecules, analogous to the scanning tunnelling microscope (STM)-based break-junction scheme 8 that has now been widely adopted to perform conductance measurements.Department of Applied Physics and Applied Mathematics, Columbia University, New York, New York 10027, USA. *e-mail: lv2117@DOI: 10.1038/NNANO.2013.91These initial experiments relied on the so-called static mode of AFM-based force spectroscopy, where the force on the canti-lever is monitored as a function of junction elongation. I n this method the deflection of the AFM cantilever is directly related to the force on the junction by Hooke’s law (force = cantilever stiff-ness × cantilever deflection). Concurrently, advances in dynamic force spectroscopy — particularly the introduction of the ‘q-Plus’ configuration 34 that utilizes a very stiff tuning fork as a force sen-sor — are enabling high-resolution measurements of atomic-size junctions. In this technique, the frequency shift of an AFM cantilever under forced near-resonance oscillation is measuredas a function of junction elongation. This frequency shift can be related to the gradient of the tip–sample force. The underlying advantage of this approach is that frequency-domain measure-ments of high-Q resonators is significantly easier to carry out with high precision. However, in contrast to the static mode, recover-ing the junction force from frequency shifts — especially in the presence of dissipation and dynamic structural changes during junction elongation experiments — is non-trivial and a detailed understanding remains to be developed 35.The most basic information that can be determined throughsimultaneous measurement of force and conductance in metalThermoelectricsSpintronics andMechanicsOptoelectronicsHotColdFigure 1 | Probing multiple properties of single-molecule junctions. phenomena in addition to demonstrations of quantum mechanical spin- and interference-dependent transport concepts for which there are no analogues in conventional electronics.contacts is the relation between the measured current and force. An experimental study by Ternes et al.36 attempted to resolve a long-standing theoretical prediction 37 that indicated that both the tunnelling current and force between two atomic-scale metal contacts scale similarly with distance (recently revisited by Jelinek et al.38). Using the dynamic force microscopy technique, Ternes et al. effectively probed the interplay between short-range forces and conductance under ultrahigh-vacuum conditions at liquid helium temperatures. As illustrated in Fig. 2a, the tunnel-ling current through the gap between the metallic AFM probe and the substrate, and the force on the cantilever were recorded, and both were found to decay exponentially with increasing distance with nearly the same decay constant. Although an exponential decay in current with distance is easily explained by considering an orbital overlap of the tip and sample wavefunctions through a tunnel barrier using Simmons’ model 39, the exponential decay in the short-range forces indicated that perhaps the same orbital controlled the interatomic short-range forces (Fig. 2b).Using such dynamic force microscopy techniques, research-ers have also studied, under ultrahigh-vacuum conditions, forces and conductance across junctions with diatomic adsorbates such as CO (refs 40,41) and more recently with fullerenes 42, address-ing the interplay between electronic transport, binding ener-getics and structural evolution. I n one such experiment, Tautz and coworkers 43 have demonstrated simultaneous conduct-ance and stiffness measurements during the lifting of a PTCDA (3,4,9,10-perylene-tetracarboxylicacid-dianhydride) molecule from a Ag(111) substrate using the dynamic mode method with an Ag-covered tungsten AFM tip. The authors were able to follow the lifting process (Fig. 2c,d) monitoring the junction stiffness as the molecule was peeled off the surface to yield a vertically bound molecule, which could also be characterized electronically to determine the conductance through the vertical metal–molecule–metal junction with an idealized geometry. These measurements were supported by force field-based model calculations (Fig. 2c and dashed black line in Fig. 2d), presenting a way to correlate local geometry to the electronic transport.Extending the work from metal point contacts, ambient meas-urements of force and conductance across single-molecule junc-tions have been carried out using the static AFM mode 33. These measurements allow correlation of the bond rupture forces with the chemistry of the linker group and molecular backbone. Single-molecule junctions are formed between a Au-metal sub-strate and a Au-coated cantilever in an environment of molecules. Measurements of current through the junction under an applied bias determine conductance, while simultaneous measurements of cantilever deflection relate to the force applied across the junction as shown in Fig. 2e. Although measurements of current throughzF zyxCantileverIVabConductance G (G 0)1 2 3Tip–sample distance d (Å)S h o r t -r a n g e f o r c e F z (n N )10−310−210−11110−110−210−3e10−410−210C o n d u c t a n c e (G 0)Displacement86420Force (nN)0.5 nm420−2F o r c e (n N )−0.4−0.200.20.4Displacement (nm)SSfIncreasing rupture forcegc(iv)(i)(iii)(ii)Low HighCounts d9630−3d F /d z (n N n m −1)(i)(iv)(iii)(ii)A p p r o a chL i ft i n g110−210−4G (2e 2/h )2051510z (Å)H 2NNH 2H 2NNH 2NNFigure 2 | Simultaneous measurements of electronic transport and mechanics. a , A conducting AFM set-up with a stiff probe (shown schematically) enabled the atomic-resolution imaging of a Pt adsorbate on a Pt(111) surface (tan colour topography), before the simultaneous measurement of interatomic forces and currents. F z , short-range force. b , Semilogarithmic plot of tunnelling conductance and F z measured over the Pt atom. A similar decay constant for current and force as a function of interatomic distance is seen. The blue dashed lines are exponential fits to the data. c , Structural snapshots showing a molecular mechanics simulation of a PTCDA molecule held between a Ag substrate and tip (read right to left). It shows the evolution of the Ag–PTCDA–Ag molecular junction as a function of tip–surface distance. d , Upper panel shows experimental stiffness (d F /d z ) measurements during the lifting process performed with a conducting AFM. The calculated values from the simulation are overlaid (dashed black line). Lower panel shows simultaneously measured conductance (G ). e , Simultaneously measured conductance (red) and force (blue) measurements showing evolution of a molecular junction as a function of junction elongation. A Au point contact is first formed, followed by the formation of a single-molecule junction, which then ruptures on further elongation. f , A two-dimensional histogram of thousands of single-molecule junctionrupture events (for 1,4-bis(methyl sulphide) butane; inset), constructed by redefining the rupture location as the zero displacement point. The most frequently measured rupture force is the drop in force (shown by the double-headed arrow) at the rupture location in the statistically averaged force trace (overlaid black curve). g , Beyond the expected dependence on the terminal group, the rupture force is also sensitive to the molecular backbone, highlighting the interplay between chemical structure and mechanics. In the case of nitrogen-terminated molecules, rupture force increases fromaromatic amines to aliphatic amines and the highest rupture force is for molecules with pyridyl moieties. Figure reproduced with permission from: a ,b , ref. 36, © 2011 APS; c ,d , ref. 43, © 2011 APS.DOI: 10.1038/NNANO.2013.91such junctions are easily accomplished using standard instru-mentation, measurements of forces with high resolution are not straightforward. This is because a rather stiff cantilever (with a typical spring constant of ~50 N m−1) is typically required to break the Au point contact that is first formed between the tip and sub-strate, before the molecular junctions are created. The force reso-lution is then limited by the smallest deflection of the cantilever that can be measured. With a custom-designed system24 our group has achieved a cantilever displacement resolution of ~2 pm (com-pare with Au atomic diameter of ~280 pm) using an optical detec-tion scheme, allowing the force noise floor of the AFM set-up to be as low as 0.1 nN even with these stiff cantilevers (Fig. 2e). With this system, and a novel analysis technique using two-dimensional force–displacement histograms as illustrated in Fig. 2f, we have been able to systematically probe the influence of the chemical linker group44,45 and the molecular backbone46 on single-molecule junction rupture force as illustrated in Fig. 2g.Significant future opportunities with force measurements exist for investigations that go beyond characterizations of the junc-tion rupture force. In two independent reports, one by our group47 and another by Wagner et al.48, force measurements were used to quantitatively measure the contribution of van der Waals interac-tions at the single-molecule level. Wagner et al. used the stiffness data from the lifting of PTCDA molecules on a Au(111) surface, and fitted it to the stiffness calculated from model potentials to estimate the contribution of the various interactions between the molecule and the surface48. By measuring force and conductance across single 4,4’-bipyridine molecules attached to Au electrodes, we were able to directly quantify the contribution of van der Waals interactions to single-molecule-junction stiffness and rupture force47. These experimental measurements can help benchmark the several theoretical frameworks currently under development aiming to reliably capture van der Waals interactions at metal/ organic interfaces due to their importance in diverse areas includ-ing catalysis, electronic devices and self-assembly.In most of the experiments mentioned thus far, the measured forces were typically used as a secondary probe of junction prop-erties, instead relying on the junction conductance as the primary signature for the formation of the junction. However, as is the case in large biological molecules49, forces measured across single-mol-ecule junctions can also provide the primary signature, thereby making it possible to characterize non-conducting molecules that nonetheless do form junctions. Furthermore, molecules pos-sess many internal degrees of motion (including vibrations and rotations) that can directly influence the electronic transport50, and the measurement of forces with such molecules can open up new avenues for mechanochemistry51. This potential of using force measurements to elucidate the fundamentals of electronic transport and binding interactions at the single-molecule level is prompting new activity in this area of research52–54. Optoelectronics and optical spectroscopyAddressing optical properties and understanding their influence on electronic transport in individual molecular-scale devices, col-lectively referred to as ‘molecular optoelectronics’, is an area with potentially important applications55. However, the fundamental mismatch between the optical (typically, approximately at the micrometre scale) and molecular-length scales has historically presented a barrier to experimental investigations. The motiva-tions for single-molecule optoelectronic studies are twofold: first, optical spectroscopies (especially Raman spectroscopy) could lead to a significantly better characterization of the local junction structure. The nanostructured metallic electrodes used to real-ize single-molecule junctions are coincidentally some of the best candidates for local field enhancement due to plasmons (coupled excitations of surface electrons and incident photons). This there-fore provides an excellent opportunity for understanding the interaction of plasmons with molecules at the nanoscale. Second, controlling the electronic transport properties using light as an external stimulus has long been sought as an attractive alternative to a molecular-scale field-effect transistor.Two independent groups have recently demonstrated simulta-neous optical and electrical measurements on molecular junctions with the aim of providing structural information using an optical probe. First, Ward et al.56 used Au nanogaps formed by electromi-gration57 to create molecular junctions with a few molecules. They then irradiated these junctions with a laser operating at a wavelength that is close to the plasmon resonance of these Au nanogaps to observe a Raman signal attributable to the molecules58 (Fig. 3a). As shown in Fig. 3b, they observed correlations between the intensity of the Raman features and magnitude of the junction conductance, providing direct evidence that Raman signatures could be used to identify junction structures. They later extended this experimental approach to estimate vibrational and electronic heating in molecu-lar junctions59. For this work, they measured the ratio of the Raman Stokes and anti-Stokes intensities, which were then related to the junction temperature as a function of the applied bias voltage. They found that the anti-Stokes intensity changed with bias voltage while the Stokes intensity remained constant, indicating that the effective temperature of the Raman-active mode was affected by passing cur-rent through the junction60. Interestingly, Ward et al. found that the vibrational mode temperatures exceeded several hundred kelvin, whereas earlier work by Tao and co-workers, who used models for junction rupture derived from biomolecule research, had indicated a much smaller value (~10 K) for electronic heating61. Whether this high temperature determined from the ratio of the anti-Stokes to Stokes intensities indicates that the electronic temperature is also similarly elevated is still being debated55, however, one can definitely conclude that such measurements under a high bias (few hundred millivolts) are clearly in a non-equilibrium transport regime, and much more research needs to be performed to understand the details of electronic heating.Concurrently, Liu et al.62 used the STM-based break-junction technique8 and combined this with Raman spectroscopy to per-form simultaneous conductance and Raman measurements on single-molecule junctions formed between a Au STM tip and a Au(111) substrate. They coupled a laser to a molecular junction as shown in Fig. 3c with a 4,4’-bipyridine molecule bridging the STM tip (top) and the substrate (bottom). Pyridines show clear surface-enhanced Raman signatures on metal58, and 4,4’-bipy-ridine is known to form single-molecule junctions in the STM break-junction set-up8,15. Similar to the study of Ward et al.56, Liu et al.62 found that conducting molecular junctions had a Raman signature that was distinct from the broken molecu-lar junctions. Furthermore, the authors studied the spectra of 4,4’-bipyridine at different bias voltages, ranging from 10 to 800 mV, and reported a reversible splitting of the 1,609 cm–1 peak (Fig. 3d). Because this Raman signature is due to a ring-stretching mode, they interpreted this splitting as arising from the break-ing of the degeneracy between the rings connected to the source and drain electrodes at high biases (Fig. 3c). Innovative experi-ments such as these have demonstrated that there is new physics to be learned through optical probing of molecular junctions, and are initiating further interest in understanding the effect of local structure and vibrational effects on electronic transport63. Experiments that probe electroluminescence — photon emis-sion induced by a tunnelling current — in these types of molec-ular junction can also offer insight into structure–conductance correlations. Ho and co-workers have demonstrated simultaneous measurement of differential conductance and photon emissionDOI: 10.1038/NNANO.2013.91from individual molecules at a submolecular-length scale using an STM 64,65. Instead of depositing molecules directly on a metal sur-face, they used an insulating layer to decouple the molecule from the metal 64,65 (Fig. 3e). This critical factor, combined with the vac-uum gap with the STM tip, ensures that the metal electrodes do not quench the radiated photons, and therefore the emitted photons carry molecular fingerprints. Indeed, the experimental observation of molecular electroluminescence of C 60 monolayers on Au(110) by Berndt et al.66 was later attributed to plasmon-mediated emission of the metallic electrodes, indirectly modulated by the molecule 67. The challenge of finding the correct insulator–molecule combination and performing the experiments at low temperature makes electro-luminescence relatively uncommon compared with the numerous Raman studies; however, progress is being made on both theoretical and experimental fronts to understand and exploit emission pro-cesses in single-molecule junctions 68.Beyond measurements of the Raman spectra of molecular junctions, light could be used to control transport in junctions formed with photochromic molecular backbones that occur in two (or more) stable and optically accessible states. Some common examples include azobenzene derivatives, which occur in a cis or trans form, as well as diarylene compounds that can be switched between a conducting conjugated form and a non-conducting cross-conjugated form 69. Experiments probing the conductance changes in molecular devices formed with such compounds have been reviewed in depth elsewhere 70,71. However, in the single-mol-ecule context, there are relatively few examples of optical modula-tion of conductance. To a large extent, this is due to the fact that although many molecular systems are known to switch reliably in solution, contact to metallic electrodes can dramatically alter switching properties, presenting a significant challenge to experi-ments at the single-molecule level.Two recent experiments have attempted to overcome this chal-lenge and have probed conductance changes in single-molecule junctions while simultaneously illuminating the junctions with visible light 72,73. Battacharyya et al.72 used a porphyrin-C 60 ‘dyad’ molecule deposited on an indium tin oxide (I TO) substrate to demonstrate the light-induced creation of an excited-state mol-ecule with a different conductance. The unconventional transpar-ent ITO electrode was chosen to provide optical access while also acting as a conducting electrode. The porphyrin segment of the molecule was the chromophore, whereas the C 60 segment served as the electron acceptor. The authors found, surprisingly, that the charge-separated molecule had a much longer lifetime on ITO than in solution. I n the break-junction experiments, the illuminated junctions showed a conductance feature that was absent without1 μm Raman shift (cm –1)1,609 cm –1(–)Source 1,609 cm–1Drain (+)Low voltage High voltageMgPNiAl(110)STM tip (Ag)VacuumThin alumina 1.4 1.5 1.6 1.701020 3040200400Photon energy (eV)3.00 V 2.90 V 2.80 V 2.70 V 2.60 V2.55 V 2.50 VP h o t o n c o u n t s (a .u .)888 829 777731Wavelength (nm)Oxideacebd f Raman intensity (CCD counts)1,5001,00050000.40.30.20.10.01,590 cm −11,498 cm −1d I /d V (μA V –1)1,609 cm –11,631 cm–11 μm1 μmTime (s)Figure 3 | Simultaneous studies of optical effects and transport. a , A scanning electron micrograph (left) of an electromigrated Au junction (light contrast) lithographically defined on a Si substrate (darker contrast). The nanoscale gap results in a ‘hot spot’ where Raman signals are enhanced, as seen in the optical image (right). b , Simultaneously measured differential conductance (black, bottom) and amplitudes of two molecular Raman features (blue traces, middle and top) as a function of time in a p-mercaptoaniline junction. c , Schematic representation of a bipyridine junction formed between a Au STM tip and a Au(111) substrate, where the tip enhancement from the atomically sharp STM tip results in a large enhancement of the Raman signal. d , The measured Raman spectra as a function of applied bias indicate breaking of symmetry in the bound molecule. e , Schematic representation of a Mg-porphyrin (MgP) molecule sandwiched between a Ag STM tip and a NiAl(110) substrate. A subnanometre alumina insulating layer is a key factor in measuring the molecular electroluminescence, which would otherwise be overshadowed by the metallic substrate. f , Emission spectra of a single Mg-porphyrin molecule as a function of bias voltage (data is vertically offset for clarity). At high biases, individual vibronic peaks become apparent. The spectra from a bare oxide layer (grey) is shown for reference. Figure reproduced with permission from: a ,b , ref. 56, © 2008 ACS; c ,d , ref. 62, © 2011 NPG; e ,f , ref. 65, © 2008 APS.DOI: 10.1038/NNANO.2013.91light, which the authors assigned to the charge-separated state. In another approach, Lara-Avila et al.73 have reported investigations of a dihydroazulene (DHA)/vinylheptafulvene (VHF) molecule switch, utilizing nanofabricated gaps to perform measurements of Au–DHA–Au single-molecule junctions. Based on the early work by Daub et al.74, DHA was known to switch to VHF under illumina-tion by 353-nm light and switch back to DHA thermally. In three of four devices, the authors observed a conductance increase after irradiating for a period of 10–20 min. In one of those three devices, they also reported reversible switching after a few hours. Although much more detailed studies are needed to establish the reliability of optical single-molecule switches, these experiments provide new platforms to perform in situ investigations of single-molecule con-ductance under illumination.We conclude this section by briefly pointing to the rapid pro-gress occurring in the development of optical probes at the single-molecule scale, which is also motivated by the tremendous interest in plasmonics and nano-optics. As mentioned previously, light can be coupled into nanoscale gaps, overcoming experimental chal-lenges such as local heating. Banerjee et al.75 have exploited these concepts to demonstrate plasmon-induced electrical conduction in a network of Au nanoparticles that form metal–molecule–metal junctions between them (Fig. 3f). Although not a single-molecule measurement, the control of molecular conductance through plas-monic coupling can benefit tremendously from the diverse set of new concepts under development in this area, such as nanofabri-cated transmission lines 76, adiabatic focusing of surface plasmons, electrical excitation of surface plasmons and nanoparticle optical antennas. The convergence of plasmonics and electronics at the fundamental atomic- and molecular-length scales can be expected to provide significant opportunities for new studies of light–mat-ter interaction 77–79.Thermoelectric characterization of single-molecule junctions Understanding the electronic response to heating in a single-mole-cule junction is not only of basic scientific interest; it can have a tech-nological impact by improving our ability to convert wasted heat into usable electricity through the thermoelectric effect, where a temper-ature difference between two sides of a device induces a voltage drop across it. The efficiency of such a device depends on its thermopower (S ; also known as the Seebeck coefficient), its electric and thermal conductivity 80. Strategies for increasing the efficiency of thermoelec-tric devices turned to nanoscale devices a decade ago 81, where one could, in principle, increase the electronic conductivity and ther-mopower while independently minimizing the thermal conductiv-ity 82. This has motivated the need for a fundamental understandingof thermoelectrics at the single-molecule level 83, and in particular, the measurement of the Seebeck coefficient in such junctions. The Seebeck coefficient, S = −(ΔV /ΔT )|I = 0, determines the magnitude of the voltage developed across the junction when a temperature dif-ference ΔT is applied, as illustrated in Fig. 4a; this definition holds both for bulk devices and for single-molecule junctions. If an addi-tional external voltage ΔV exists across the junction, then the cur-rent I through the junction is given by I = G ΔV + GS ΔT where G is the junction conductance 83. Transport through molecular junctions is typically in the coherent regime where conductance, which is pro-portional to the electronic transmission probability, is given by the Landauer formula 84. The Seebeck coefficient at zero applied voltage is then related to the derivative of the transmission probability at the metal Fermi energy (in the off-resonance limit), with, S = −∂E ∂ln( (E ))π2k 2B T E 3ewhere k B is the Boltzmann constant, e is the charge of the electron, T (E ) is the energy-dependent transmission function and E F is the Fermi energy. When the transmission function for the junction takes on a simple Lorentzian form 85, and transport is in the off-resonance limit, the sign of S can be used to deduce the nature of charge carriers in molecular junctions. In such cases, a positive S results from hole transport through the highest occupied molecu-lar orbital (HOMO) whereas a negative S indicates electron trans-port through the lowest unoccupied molecular orbital (LUMO). Much work has been performed on investigating the low-bias con-ductance of molecular junctions using a variety of chemical linker groups 86–89, which, in principle, can change the nature of charge carriers through the junction. Molecular junction thermopower measurements can thus be used to determine the nature of charge carriers, correlating the backbone and linker chemistry with elec-tronic aspects of conduction.Experimental measurements of S and conductance were first reported by Ludoph and Ruitenbeek 90 in Au point contacts at liquid helium temperatures. This work provided a method to carry out thermoelectric measurements on molecular junctions. Reddy et al.91 implemented a similar technique in the STM geome-try to measure S of molecular junctions, although due to electronic limitations, they could not simultaneously measure conductance. They used thiol-terminated oligophenyls with 1-3-benzene units and found a positive S that increased with increasing molecular length (Fig. 4b). These pioneering experiments allowed the iden-tification of hole transport through thiol-terminated molecular junctions, while also introducing a method to quantify S from statistically significant datasets. Following this work, our group measured the thermoelectric current through a molecular junction held under zero external bias voltage to determine S and the con-ductance through the same junction at a finite bias to determine G (ref. 92). Our measurements showed that amine-terminated mol-ecules conduct through the HOMO whereas pyridine-terminatedmolecules conduct through the LUMO (Fig. 4b) in good agree-ment with calculations.S has now been measured on a variety of molecular junctionsdemonstrating both hole and electron transport 91–95. Although the magnitude of S measured for molecular junctions is small, the fact that it can be tuned by changing the molecule makes these experiments interesting from a scientific perspective. Future work on the measurements of the thermal conductance at the molecu-lar level can be expected to establish a relation between chemical structure and the figure of merit, which defines the thermoelec-tric efficiencies of such devices and determines their viability for practical applications.SpintronicsWhereas most of the explorations of metal–molecule–metal junc-tions have been motivated by the quest for the ultimate minia-turization of electronic components, the quantum-mechanical aspects that are inherent to single-molecule junctions are inspir-ing entirely new device concepts with no classical analogues. In this section, we review recent experiments that demonstrate the capability of controlling spin (both electronic and nuclear) in single-molecule devices 96. The early experiments by the groups of McEuen and Ralph 97, and Park 98 in 2002 explored spin-depend-ent transport and the Kondo effect in single-molecule devices, and this topic has recently been reviewed in detail by Scott and Natelson 99. Here, we focus on new types of experiment that are attempting to control the spin state of a molecule or of the elec-trons flowing through the molecular junction. These studies aremotivated by the appeal of miniaturization and coherent trans-port afforded by molecular electronics, combined with the great potential of spintronics to create devices for data storage and quan-tum computation 100. The experimental platforms for conducting DOI: 10.1038/NNANO.2013.91。
湍流燃烧模型
Contents
1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 195 2. Balance equations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 196
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D. Veynante, L. Vervisch / Progress in Energy and Combustion Science 28 (2002) 193±266
6. Tools for turbulent combustion modeling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 212 6.1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 212 6.2. Scalar dissipation rate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 214 6.3. Geometrical description . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 214 6.3.1. G-®eld equation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 214 6.3.2. Flame surface density description . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 216 6.3.3. Flame wrinkling description . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 218 6.4. Statistical approaches: probability density function . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 218 6.4.1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 218 6.4.2. Presumed probability density functions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 219 6.4.3. Pdf balance equation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 219 6.4.4. Joint velocity/concentrations pdf . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 221 6.4.5. Conditional moment closure (CMC) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 221 6.5. Similarities and links between the tools . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 221
半导体一些术语的中英文对照
半导体一些术语的中英文对照离子注入机ion implanterLSS理论Lindhand Scharff and Schiott theory 又称“林汉德—斯卡夫—斯高特理论".沟道效应channeling effect射程分布range distribution深度分布depth distribution投影射程projected range阻止距离stopping distance阻止本领stopping power标准阻止截面standard stopping cross section 退火annealing激活能activation energy等温退火isothermal annealing激光退火laser annealing应力感生缺陷stress-induced defect择优取向preferred orientation制版工艺mask—making technology图形畸变pattern distortion初缩first minification精缩final minification母版master mask铬版chromium plate干版dry plate乳胶版emulsion plate透明版see—through plate高分辨率版high resolution plate,HRP超微粒干版plate for ultra-microminiaturization 掩模mask掩模对准mask alignment对准精度alignment precision光刻胶photoresist又称“光致抗蚀剂”。
负性光刻胶negative photoresist正性光刻胶positive photoresist无机光刻胶inorganic resist多层光刻胶multilevel resist电子束光刻胶electron beam resistX射线光刻胶X-ray resist刷洗scrubbing甩胶spinning涂胶photoresist coating后烘postbaking光刻photolithographyX射线光刻X-ray lithography电子束光刻electron beam lithography离子束光刻ion beam lithography深紫外光刻deep-UV lithography光刻机mask aligner投影光刻机projection mask aligner曝光exposure接触式曝光法contact exposure method接近式曝光法proximity exposure method光学投影曝光法optical projection exposure method 电子束曝光系统electron beam exposure system分步重复系统step-and—repeat system显影development线宽linewidth去胶stripping of photoresist氧化去胶removing of photoresist by oxidation等离子[体]去胶removing of photoresist by plasma 刻蚀etching干法刻蚀dry etching反应离子刻蚀reactive ion etching, RIE各向同性刻蚀isotropic etching各向异性刻蚀anisotropic etching反应溅射刻蚀reactive sputter etching离子铣ion beam milling又称“离子磨削”。
Principles of Plasma Discharges and Materials Processing9
CHAPTER8MOLECULAR COLLISIONS8.1INTRODUCTIONBasic concepts of gas-phase collisions were introduced in Chapter3,where we described only those processes needed to model the simplest noble gas discharges: electron–atom ionization,excitation,and elastic scattering;and ion–atom elastic scattering and resonant charge transfer.In this chapter we introduce other collisional processes that are central to the description of chemically reactive discharges.These include the dissociation of molecules,the generation and destruction of negative ions,and gas-phase chemical reactions.Whereas the cross sections have been measured reasonably well for the noble gases,with measurements in reasonable agreement with theory,this is not the case for collisions in molecular gases.Hundreds of potentially significant collisional reactions must be examined in simple diatomic gas discharges such as oxygen.For feedstocks such as CF4/O2,SiH4/O2,etc.,the complexity can be overwhelming.Furthermore,even when the significant processes have been identified,most of the cross sections have been neither measured nor calculated. Hence,one must often rely on estimates based on semiempirical or semiclassical methods,or on measurements made on molecules analogous to those of interest. As might be expected,data are most readily available for simple diatomic and polyatomic gases.Principles of Plasma Discharges and Materials Processing,by M.A.Lieberman and A.J.Lichtenberg. ISBN0-471-72001-1Copyright#2005John Wiley&Sons,Inc.235236MOLECULAR COLLISIONS8.2MOLECULAR STRUCTUREThe energy levels for the electronic states of a single atom were described in Chapter3.The energy levels of molecules are more complicated for two reasons. First,molecules have additional vibrational and rotational degrees of freedom due to the motions of their nuclei,with corresponding quantized energies E v and E J. Second,the energy E e of each electronic state depends on the instantaneous con-figuration of the nuclei.For a diatomic molecule,E e depends on a single coordinate R,the spacing between the two nuclei.Since the nuclear motions are slow compared to the electronic motions,the electronic state can be determined for anyfixed spacing.We can therefore represent each quantized electronic level for a frozen set of nuclear positions as a graph of E e versus R,as shown in Figure8.1.For a mole-cule to be stable,the ground(minimum energy)electronic state must have a minimum at some value R1corresponding to the mean intermolecular separation (curve1).In this case,energy must be supplied in order to separate the atoms (R!1).An excited electronic state can either have a minimum( R2for curve2) or not(curve3).Note that R2and R1do not generally coincide.As for atoms, excited states may be short lived(unstable to electric dipole radiation)or may be metastable.Various electronic levels may tend to the same energy in the unbound (R!1)limit. Array FIGURE8.1.Potential energy curves for the electronic states of a diatomic molecule.For diatomic molecules,the electronic states are specifiedfirst by the component (in units of hÀ)L of the total orbital angular momentum along the internuclear axis, with the symbols S,P,D,and F corresponding to L¼0,+1,+2,and+3,in analogy with atomic nomenclature.All but the S states are doubly degenerate in L.For S states,þandÀsuperscripts are often used to denote whether the wave function is symmetric or antisymmetric with respect to reflection at any plane through the internuclear axis.The total electron spin angular momentum S (in units of hÀ)is also specified,with the multiplicity2Sþ1written as a prefixed superscript,as for atomic states.Finally,for homonuclear molecules(H2,N2,O2, etc.)the subscripts g or u are written to denote whether the wave function is sym-metric or antisymmetric with respect to interchange of the nuclei.In this notation, the ground states of H2and N2are both singlets,1Sþg,and that of O2is a triplet,3SÀg .For polyatomic molecules,the electronic energy levels depend on more thanone nuclear coordinate,so Figure8.1must be generalized.Furthermore,since there is generally no axis of symmetry,the states cannot be characterized by the quantum number L,and other naming conventions are used.Such states are often specified empirically through characterization of measured optical emission spectra.Typical spacings of low-lying electronic energy levels range from a few to tens of volts,as for atoms.Vibrational and Rotational MotionsUnfreezing the nuclear vibrational and rotational motions leads to additional quan-tized structure on smaller energy scales,as illustrated in Figure8.2.The simplest (harmonic oscillator)model for the vibration of diatomic molecules leads to equally spaced quantized,nondegenerate energy levelse E v¼hÀv vib vþ1 2(8:2:1)where v¼0,1,2,...is the vibrational quantum number and v vib is the linearized vibration frequency.Fitting a quadratic functione E v¼12k vib(RÀ R)2(8:2:2)near the minimum of a stable energy level curve such as those shown in Figure8.1, we can estimatev vib%k vibm Rmol1=2(8:2:3)where k vib is the“spring constant”and m Rmol is the reduced mass of the AB molecule.The spacing hÀv vib between vibrational energy levels for a low-lying8.2MOLECULAR STRUCTURE237stable electronic state is typically a few tenths of a volt.Hence for molecules in equi-librium at room temperature (0.026V),only the v ¼0level is significantly popula-ted.However,collisional processes can excite strongly nonequilibrium vibrational energy levels.We indicate by the short horizontal line segments in Figure 8.1a few of the vibrational energy levels for the stable electronic states.The length of each segment gives the range of classically allowed vibrational motions.Note that even the ground state (v ¼0)has a finite width D R 1as shown,because from(8.2.1),the v ¼0state has a nonzero vibrational energy 1h Àv vib .The actual separ-ation D R about Rfor the ground state has a Gaussian distribution,and tends toward a distribution peaked at the classical turning points for the vibrational motion as v !1.The vibrational motion becomes anharmonic and the level spa-cings tend to zero as the unbound vibrational energy is approached (E v !D E 1).FIGURE 8.2.Vibrational and rotational levels of two electronic states A and B of a molecule;the three double arrows indicate examples of transitions in the pure rotation spectrum,the rotation–vibration spectrum,and the electronic spectrum (after Herzberg,1971).238MOLECULAR COLLISIONSFor E v.D E1,the vibrational states form a continuum,corresponding to unbound classical motion of the nuclei(breakup of the molecule).For a polyatomic molecule there are many degrees of freedom for vibrational motion,leading to a very compli-cated structure for the vibrational levels.The simplest(dumbbell)model for the rotation of diatomic molecules leads to the nonuniform quantized energy levelse E J¼hÀ22I molJ(Jþ1)(8:2:4)where I mol¼m Rmol R2is the moment of inertia and J¼0,1,2,...is the rotational quantum number.The levels are degenerate,with2Jþ1states for the J th level. The spacing between rotational levels increases with J(see Figure8.2).The spacing between the lowest(J¼0to J¼1)levels typically corresponds to an energy of0.001–0.01V;hence,many low-lying levels are populated in thermal equilibrium at room temperature.Optical EmissionAn excited molecular state can decay to a lower energy state by emission of a photon or by breakup of the molecule.As shown in Figure8.2,the radiation can be emitted by a transition between electronic levels,between vibrational levels of the same electronic state,or between rotational levels of the same electronic and vibrational state;the radiation typically lies within the optical,infrared,or microwave frequency range,respectively.Electric dipole radiation is the strongest mechanism for photon emission,having typical transition times of t rad 10À9s,as obtained in (3.4.13).The selection rules for electric dipole radiation areDL¼0,+1(8:2:5a)D S¼0(8:2:5b) In addition,for transitions between S states the only allowed transitions areSþÀ!Sþand SÀÀ!SÀ(8:2:6) and for homonuclear molecules,the only allowed transitions aregÀ!u and uÀ!g(8:2:7) Hence homonuclear diatomic molecules do not have a pure vibrational or rotational spectrum.Radiative transitions between electronic levels having many different vibrational and rotational initial andfinal states give rise to a structure of emission and absorption bands within which a set of closely spaced frequencies appear.These give rise to characteristic molecular emission and absorption bands when observed8.2MOLECULAR STRUCTURE239using low-resolution optical spectrometers.As for atoms,metastable molecular states having no electric dipole transitions to lower levels also exist.These have life-times much exceeding10À6s;they can give rise to weak optical band structures due to magnetic dipole or electric quadrupole radiation.Electric dipole radiation between vibrational levels of the same electronic state is permitted for molecules having permanent dipole moments.In the harmonic oscillator approximation,the selection rule is D v¼+1;weaker transitions D v¼+2,+3,...are permitted for anharmonic vibrational motion.The preceding description of molecular structure applies to molecules having arbi-trary electronic charge.This includes neutral molecules AB,positive molecular ions ABþ,AB2þ,etc.and negative molecular ions ABÀ.The potential energy curves for the various electronic states,regardless of molecular charge,are commonly plotted on the same diagram.Figures8.3and8.4give these for some important electronic statesof HÀ2,H2,and Hþ2,and of OÀ2,O2,and Oþ2,respectively.Examples of both attractive(having a potential energy minimum)and repulsive(having no minimum)states can be seen.The vibrational levels are labeled with the quantum number v for the attrac-tive levels.The ground states of both Hþ2and Oþ2are attractive;hence these molecular ions are stable against autodissociation(ABþ!AþBþor AþþB).Similarly,the ground states of H2and O2are attractive and lie below those of Hþ2and Oþ2;hence they are stable against autodissociation and autoionization(AB!ABþþe).For some molecules,for example,diatomic argon,the ABþion is stable but the AB neutral is not stable.For all molecules,the AB ground state lies below the ABþground state and is stable against autoionization.Excited states can be attractive or repulsive.A few of the attractive states may be metastable;some examples are the 3P u state of H2and the1D g,1Sþgand3D u states of O2.Negative IonsRecall from Section7.2that many neutral atoms have a positive electron affinity E aff;that is,the reactionAþeÀ!AÀis exothermic with energy E aff(in volts).If E aff is negative,then AÀis unstable to autodetachment,AÀ!Aþe.A similar phenomenon is found for negative molecular ions.A stable ABÀion exists if its ground(lowest energy)state has a potential minimum that lies below the ground state of AB.This is generally true only for strongly electronegative gases having large electron affinities,such as O2 (E aff%1:463V for O atoms)and the halogens(E aff.3V for the atoms).For example,Figure8.4shows that the2P g ground state of OÀ2is stable,with E aff% 0:43V for O2.For weakly electronegative or for electropositive gases,the minimum of the ground state of ABÀgenerally lies above the ground state of AB,and ABÀis unstable to autodetachment.An example is hydrogen,which is weakly electronegative(E aff%0:754V for H atoms).Figure8.3shows that the2Sþu ground state of HÀ2is unstable,although the HÀion itself is stable.In an elec-tropositive gas such as N2(E aff.0),both NÀ2and NÀare unstable. 240MOLECULAR COLLISIONS8.3ELECTRON COLLISIONS WITH MOLECULESThe interaction time for the collision of a typical (1–10V)electron with a molecule is short,t c 2a 0=v e 10À16–10À15s,compared to the typical time for a molecule to vibrate,t vib 10À14–10À13s.Hence for electron collisional excitation of a mole-cule to an excited electronic state,the new vibrational (and rotational)state canbeFIGURE 8.3.Potential energy curves for H À2,H 2,and H þ2.(From Jeffery I.Steinfeld,Molecules and Radiation:An Introduction to Modern Molecular Spectroscopy ,2d ed.#MIT Press,1985.)8.3ELECTRON COLLISIONS WITH MOLECULES 241FIGURE 8.4.Potential energy curves for O À2,O 2,and O þ2.(From Jeffery I.Steinfeld,Molecules and Radiation:An Introduction to Modern Molecular Spectroscopy ,2d ed.#MIT Press,1985.)242MOLECULAR COLLISIONS8.3ELECTRON COLLISIONS WITH MOLECULES243 determined by freezing the nuclear motions during the collision.This is known as the Franck–Condon principle and is illustrated in Figure8.1by the vertical line a,showing the collisional excitation atfixed R to a high quantum number bound vibrational state and by the vertical line b,showing excitation atfixed R to a vibra-tionally unbound state,in which breakup of the molecule is energetically permitted. Since the typical transition time for electric dipole radiation(t rad 10À9–10À8s)is long compared to the dissociation( vibrational)time t diss,excitation to an excited state will generally lead to dissociation when it is energetically permitted.Finally, we note that the time between collisions t c)t rad in typical low-pressure processing discharges.Summarizing the ordering of timescales for electron–molecule collisions,we havet at t c(t vib t diss(t rad(t cDissociationElectron impact dissociation,eþABÀ!AþBþeof feedstock gases plays a central role in the chemistry of low-pressure reactive discharges.The variety of possible dissociation processes is illustrated in Figure8.5.In collisions a or a0,the v¼0ground state of AB is excited to a repulsive state of AB.The required threshold energy E thr is E a for collision a and E a0for Array FIGURE8.5.Illustrating the variety of dissociation processes for electron collisions with molecules.collision a0,and it leads to an energy after dissociation lying between E aÀE diss and E a0ÀE diss that is shared among the dissociation products(here,A and B). Typically,E aÀE diss few volts;consequently,hot neutral fragments are typically generated by dissociation processes.If these hot fragments hit the substrate surface, they can profoundly affect the process chemistry.In collision b,the ground state AB is excited to an attractive state of AB at an energy E b that exceeds the binding energy E diss of the AB molecule,resulting in dissociation of AB with frag-ment energy E bÀE diss.In collision b0,the excitation energy E b0¼E diss,and the fragments have low energies;hence this process creates fragments having energies ranging from essentially thermal energies up to E bÀE diss few volts.In collision c,the AB atom is excited to the bound excited state ABÃ(labeled5),which sub-sequently radiates to the unbound AB state(labeled3),which then dissociates.The threshold energy required is large,and the fragments are hot.Collision c can also lead to dissociation of an excited state by a radiationless transfer from state5to state4near the point where the two states cross:ABÃðboundÞÀ!ABÃðunboundÞÀ!AþBÃThe fragments can be both hot and in excited states.We discuss such radiationless electronic transitions in the next section.This phenomenon is known as predisso-ciation.Finally,a collision(not labeled in thefigure)to state4can lead to dis-sociation of ABÃ,again resulting in hot excited fragments.The process of electron impact excitation of a molecule is similar to that of an atom,and,consequently,the cross sections have a similar form.A simple classical estimate of the dissociation cross section for a level having excitation energy U1can be found by requiring that an incident electron having energy W transfer an energy W L lying between U1and U2to a valence electron.Here,U2is the energy of the next higher level.Then integrating the differential cross section d s[given in(3.4.20)and repeated here],d s¼pe24021Wd W LW2L(3:4:20)over W L,we obtains diss¼0W,U1pe24pe021W1U1À1WU1,W,U2pe24021W1U1À1U2W.U28>>>>>><>>>>>>:(8:3:1)244MOLECULAR COLLISIONSLetting U2ÀU1(U1and introducing voltage units W¼e E,U1¼e E1and U2¼e E2,we haves diss¼0E,E1s0EÀE11E1,E,E2s0E2ÀE1EE.E28>>>><>>>>:(8:3:2)wheres0¼pe4pe0E12(8:3:3)We see that the dissociation cross section rises linearly from the threshold energy E thr%E1to a maximum value s0(E2ÀE1)=E thr at E2and then falls off as1=E. Actually,E1and E2can depend on the nuclear separation R.In this case,(8.3.2) should be averaged over the range of R s corresponding to the ground-state vibrational energy,leading to a broadened dependence of the average cross section on energy E.The maximum cross section is typically of order10À15cm2. Typical rate constants for a single dissociation process with E thr&T e have an Arrhenius formK diss/K diss0expÀE thr T e(8:3:4)where K diss0 10À7cm3=s.However,in some cases E thr.T e.For excitation to an attractive state,an appropriate average over the fraction of the ground-state vibration that leads to dissociation must be taken.Dissociative IonizationIn addition to normal ionization,eþABÀ!ABþþ2eelectron–molecule collisions can lead to dissociative ionizationeþABÀ!AþBþþ2eThese processes,common for polyatomic molecules,are illustrated in Figure8.6.In collision a having threshold energy E iz,the molecular ion ABþis formed.Collisionsb andc occur at higher threshold energies E diz and result in dissociative ionization,8.3ELECTRON COLLISIONS WITH MOLECULES245leading to the formation of fast,positively charged ions and neutrals.These cross sections have a similar form to the Thompson ionization cross section for atoms.Dissociative RecombinationThe electron collision,e þAB þÀ!A þB Ãillustrated as d and d 0in Figure 8.6,destroys an electron–ion pair and leads to the production of fast excited neutral fragments.Since the electron is captured,it is not available to carry away a part of the reaction energy.Consequently,the collision cross section has a resonant character,falling to very low values for E ,E d and E .E d 0.However,a large number of excited states A Ãand B Ãhaving increasing principal quantum numbers n and energies can be among the reaction products.Consequently,the rate constants can be large,of order 10À7–10À6cm 3=s.Dissocia-tive recombination to the ground states of A and B cannot occur because the potential energy curve for AB þis always greater than the potential energycurveFIGURE 8.6.Illustration of dissociative ionization and dissociative recombination for electron collisions with molecules.246MOLECULAR COLLISIONSfor the repulsive state of AB.Two-body recombination for atomic ions or for mol-ecular ions that do not subsequently dissociate can only occur with emission of a photon:eþAþÀ!Aþh n:As shown in Section9.2,the rate constants are typically three tofive orders of magnitude lower than for dissociative recombination.Example of HydrogenThe example of H2illustrates some of the inelastic electron collision phenomena we have discussed.In order of increasing electron impact energy,at a threshold energy of 8:8V,there is excitation to the repulsive3Sþu state followed by dissociation into two fast H fragments carrying 2:2V/atom.At11.5V,the1Sþu bound state is excited,with subsequent electric dipole radiation in the ultraviolet region to the1Sþg ground state.At11.8V,there is excitation to the3Sþg bound state,followedby electric dipole radiation to the3Sþu repulsive state,followed by dissociation with 2:2V/atom.At12.6V,the1P u bound state is excited,with UV emission tothe ground state.At15.4V,the2Sþg ground state of Hþ2is excited,leading to the pro-duction of Hþ2ions.At28V,excitation of the repulsive2Sþu state of Hþ2leads to thedissociative ionization of H2,with 5V each for the H and Hþfragments.Dissociative Electron AttachmentThe processes,eþABÀ!AþBÀproduce negative ion fragments as well as neutrals.They are important in discharges containing atoms having positive electron affinities,not only because of the pro-duction of negative ions,but because the threshold energy for production of negative ion fragments is usually lower than for pure dissociation processes.A variety of pro-cesses are possible,as shown in Figure8.7.Since the impacting electron is captured and is not available to carry excess collision energy away,dissociative attachment is a resonant process that is important only within a narrow energy range.The maximum cross sections are generally much smaller than the hard-sphere cross section of the molecule.Attachment generally proceeds by collisional excitation from the ground AB state to a repulsive ABÀstate,which subsequently either auto-detaches or dissociates.The attachment cross section is determined by the balance between these processes.For most molecules,the dissociation energy E diss of AB is greater than the electron affinity E affB of B,leading to the potential energy curves shown in Figure8.7a.In this case,the cross section is large only for impact energies lying between a minimum value E thr,for collision a,and a maximum value E0thr for8.3ELECTRON COLLISIONS WITH MOLECULES247FIGURE 8.7.Illustration of a variety of electron attachment processes for electron collisions with molecules:(a )capture into a repulsive state;(b )capture into an attractive state;(c )capture of slow electrons into a repulsive state;(d )polar dissociation.248MOLECULAR COLLISIONScollision a 0.The fragments are hot,having energies lying between minimum and maximum values E min ¼E thr þE affB ÀE diss and E max ¼E 0thr þE af fB ÀE diss .Since the AB Àstate lies above the AB state for R ,R x ,autodetachment can occur as the mol-ecules begin to separate:AB À!AB þe.Hence the cross section for production of negative ions can be much smaller than that for excitation of the AB Àrepulsive state.As a crude estimate,for the same energy,the autodetachment rate is ffiffiffiffiffiffiffiffiffiffiffiffiffiM R =m p 100times the dissociation rate of the repulsive AB Àmolecule,where M R is the reduced mass.Hence only one out of 100excitations lead to dissociative attachment.Excitation to the AB Àbound state can also lead to dissociative attachment,as shown in Figure 8.7b .Here the cross section is significant only for E thr ,E ,E 0thr ,but the fragments can have low energies,with a minimum energy of zero and a maximum energy of E 0thr þE affB ÀE diss .Collision b,e þAB À!AB ÀÃdoes not lead to production of AB Àions because energy and momentum are not gen-erally conserved when two bodies collide elastically to form one body (see Problem3.12).Hence the excited AB ÀÃion separates,AB ÀÃÀ!e þABunless vibrational radiation or collision with a third body carries off the excess energy.These processes are both slow in low-pressure discharges (see Section 9.2).At high pressures (say,atmospheric),three-body attachment to form AB Àcan be very important.For a few molecules,such as some halogens,the electron affinity of the atom exceeds the dissociation energy of the neutral molecule,leading to the potential energy curves shown in Figure 8.7c .In this case the range of electron impact ener-gies E for excitation of the AB Àrepulsive state includes E ¼0.Consequently,there is no threshold energy,and very slow electrons can produce dissociative attachment,resulting in hot neutral and negative ion fragments.The range of R s over which auto-detachment can occur is small;hence the maximum cross sections for dissociative attachment can be as high as 10À16cm 2.A simple classical estimate of electron capture can be made using the differential scattering cross section for energy loss (3.4.20),in a manner similar to that done for dissociation.For electron capture to an energy level E 1that is unstable to autode-tachment,and with the additional constraint for capture that the incident electron energy lie within E 1and E 2¼E 1þD E ,where D E is a small energy difference characteristic of the dissociative attachment timescale,we obtain,in place of (8.3.2),s att¼0E ,E 1s 0E ÀE 1E 1E 1,E ,E 20E .E 28>><>>:(8:3:5)8.3ELECTRON COLLISIONS WITH MOLECULES 249wheres 0%p m M R 1=2e 4pe 0E 1 2(8:3:6)The factor of (m =M R )1=2roughly gives the fraction of excited states that do not auto-detach.We see that the dissociative attachment cross section rises linearly at E 1to a maximum value s 0D E =E 1and then falls abruptly to zero.As for dissociation,E 1can depend strongly on the nuclear separation R ,and (8.3.5)must be averaged over the range of E 1s corresponding to the ground state vibrational motion;e.g.,from E thr to E 0thr in Figure 8.7a .Because generally D E (E 0thr ÀE thr ,we can write (8.3.5)in the forms att %p m M R 1=2e 4pe 0 2(D E )22E 1d (E ÀE 1)(8:3:7)where d is the Dirac delta ing (8.3.7),the average over the vibrational motion can be performed,leading to a cross section that is strongly peaked lying between E thr and E 0thr .We leave the details of the calculation to a problem.Polar DissociationThe process,e þAB À!A þþB Àþeproduces negative ions without electron capture.As shown in Figure 8.7d ,the process proceeds by excitation of a polar state A þand B Àof AB Ãthat has a separ-ated atom limit of A þand B À.Hence at large R ,this state lies above the A þB ground state by the difference between the ionization potential of A and the electron affinity of B.The polar state is weakly bound at large R by the Coulomb attraction force,but is repulsive at small R .The maximum cross section and the dependence of the cross section on electron impact energy are similar to that of pure dissociation.The threshold energy E thr for polar dissociation is generally large.The measured cross section for negative ion production by electron impact in O 2is shown in Figure 8.8.The sharp peak at 6.5V is due to dissociative attachment.The variation of the cross section with energy is typical of a resonant capture process.The maximum cross section of 10À18cm 2is quite low because autode-tachment from the repulsive O À2state is strong,inhibiting dissociative attachment.The second gradual maximum near 35V is due to polar dissociation;the variation of the cross section with energy is typical of a nonresonant process.250MOLECULAR COLLISIONS。
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failure probabilities of a system undergoing random impacts according to a space-time gamma noise. Notice that the symmetrized generator ˜f (x) = Γ has symbol log(1 + |ξ |) = lim α−1 ((1 + |ξ |)α − 1),
(see e.g. [11]) and can be viewed as the weak limit of α−1 ((I − ∆1/2 )α − I ) as α goes
of (1.3) (finite-time blow up vs existence of global solutions) constitutes a natural follow-up to previous investigations, as it can be considered in a sense as a “limiting case” α → 0. Let us recall that the gamma process belongs to a special class of L´ evy pro-
then (1.1) possesses no global nontrivial solutions, and if d > dc , then (1.1) admits a 1
nontrivial global solution for all sufficiently small initial values. Critical parameters
(0,1]
[x, ∞).
a.s. and the transition kernels Pt−s (x, dy ) := P (Xt ∈ dy |Xs = x) are supported in In contrast with the Brownian and α-stable L´ evy motions, subordinators enjoy in
where ϕ is a nonnegative function, ν , σ and β are positive constants, and Γ is the pseudo-differential operator
∞
Γ f (x) =
0
(f (x + y ) − f (x))
e−y dy, y
BLOW-UP AND STABILITY OF SEMILINEAR PDE’S WITH GAMMA GENERATORS
Jos´ e Alfredo L´ opez-Mimbela
Abstract We investigate finite-time blow-up and stability of semilinear partial differen1+β tial equations of the form ∂wt /∂t = Γ wt + νtσ wt , w0 (x) = ϕ(x) ≥ 0, x ∈ R+ , where Γ is the generator of the standard gamma process and ν > 0, σ ∈ R, β > 0 are constants. We show that any initial value satisfying c 1 x−a1 ≤ ϕ(x), x > x0 for some positive constants x0 , c1 , a1 , yields a non-global solution if a1 β < 1 + σ . If ϕ(x) ≤ c2 x−a2 , x > x0 , where x0 , c2 , a2 > 0, and a2 β > 1 + σ , then the solution wt is global and satisfies 0 ≤ wt (x) ≤ Ct−a2 , x ≥ 0, for some constant C > 0. This complements the results previously obtained in [3, 10, 22] for symmetric α-stable generators. Systems of semilinear PDE’s with gamma generators are also considered.
x ν (dx) < ∞. In particular, the trajectories t → Xt (ω ) are increasing functions
general no scaling or symmetry property, nor dimensional-dependent behavior. This circumstance makes it difficult to carry out the methods in the papers quoted above to investigate (1.1), since most of those methods rely significantly on the symmetry and scaling properties of Gaussian and stable distributions. However, in the case we are considering here the transition densities of the motion process are explicitly given, and, moreover, it is known that the bridges (1.2) are beta distributed. Together with the estimates of [18] for the median of beta distributions, this allows us to obtain lower bounds for the bridge distribution of the gamma subordinator, making it possible to exploit the Feynman-Kac approach of [3] to derive criteria for finite-time blow of (1.3).
Nicolas Privault
Key words: Semilinear partial differential equations, Feynman-Kac representation, blowup of semilinear systems, gamma processes. Mathematics Subject Classification: 60H30, 35K57, 35B35, 60J57, 60E07, 60J75.
cesses called subordinators (see e.g. [2] or [21]), a subordinator being a purely nonGaussian L´ evy process {Xt } in R, whose L´ evy measure ν satisfies ν ((−∞, 0)) = 0 and
It is shown that gt (resp. ht ) grows locally to ∞ if d < dc (resp. if d = dc , and in this
Px (Xs ∈ B |Xt = y ),
0 ≤ s ≤ t,
(1.2)
of (1.1), in dimensions d ≤ dc , then follow from a classical argument that goes back to [12]. Motivated by the method developed in [3], in this paper we investigate finite-time
where L is a L´ evy generator, β > 0 is constant and ϕ ≥ 0, have been investigated
by many authors, specially in the case of the d-dimensional Laplacian L = ∆ (see [13] and [6] for surveys). When L is the fractional power ∆α = −(−∆)α/2 of the Laplacian, 0 < α ≤ 2, it was shown in a series of papers [3, 15, 17, 20, 22] that the critical parameter for blow-up of (1.1) is dc := α/β , meaning that if d ≤ dc
1+β for semilinear equations with time-dependent non-linearities of the form tσ wt (x)
were studied in [3] and [10] for L = ∆α . The case of an elliptic operator L on an exterior domain was investigated in [1] for general time-dependent reaction terms. The approaches developed in the works quoted above use subtle compaobabilistic representations of solutions [3, 15, 17, 20]. In [3] the Feynman-Kac formula is used to construct subsolutions 0 ≤ ft ≤ gt ≤ ht of (1.1), where ft = etL ϕ, and gt , ht are the mild solutions, respectively, of ∂gt = Lgt + ftβ gt , ∂t g0 = ϕ, and ∂ht β = Lht + gt ht , ∂t