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Polarization Band Effect and MEMS-Based Plasma Generation
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作者 Henggao Ding Zhongyu Hou 《Instrumentation》 2024年第2期1-8,共8页
We find that effects resulting from micro/nano scale structures can regulate space charges which excite and lead to the special electric field distribution featuring the flux convergence band structure. It is here ref... We find that effects resulting from micro/nano scale structures can regulate space charges which excite and lead to the special electric field distribution featuring the flux convergence band structure. It is here referred to as the polarization band effect, which stems from the specific field-induced interactions among atoms and molecules. The micro/nanoelectrode array structures were designed and fabricated using the non-silicon micro/nano processing technology, forming micro/nano electrode arrays-based plasma microelectromechanical systems(NPMEMS). The integrated NPMEMS device can be used to regulate the inner energy states of matters and generate plasma based on the polarization band effect, all within a single chip-size limited local area or extending into a large volume space with the deployment of a distributed array of multiple devices. Its special physical and chemical properties can be utilized to greatly improve the efficiency of potential application systems or solve mechanism-level challenges in plasma-related applications of multiple fields. 展开更多
关键词 polarization band effect MEMS micro/nanoelectrode array PLASMA
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Abnormal Polarity Effects of Streamer Discharge in Propylene Carbonate under Microsecond Pulses 被引量:2
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作者 刘宏伟 侯炎磐 +1 位作者 张自成 徐健 《Chinese Physics Letters》 SCIE CAS CSCD 2017年第7期254-257,共4页
Propylene carbonate (PC) has a great potential to be used as an energy storage medium in the compact pulsed power sources due to its high dielectric constant and large resistivity. We investigate both the positive a... Propylene carbonate (PC) has a great potential to be used as an energy storage medium in the compact pulsed power sources due to its high dielectric constant and large resistivity. We investigate both the positive and negative breakdown characteristics of PC. The streamer patterns are obtained by ultra-high-speed cameras. The experimental results show that the positive breakdown voltage of PC is about 135% higher than the negative one, which is abnormal compared with the common liquid. The shape of the positive streamer is filamentary and branchy, while the negative streamer is tree-like and less branched. According to these experimental results, a charge layer structure model at the interface between the metal electrode and liquid is presented. It is suggested that the abnormal polarity effect basically arises from the electric field strength difference in the interface between both electrodes and PC. What is more, the recombination radiation and photoionization also play an important role in the whole discharge process. 展开更多
关键词 PC Abnormal polarity effects of Streamer Discharge in Propylene Carbonate under Microsecond Pulses
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Experimental Study of Induced Polarization Effect in Unconventional Reservoir Rocks 被引量:4
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作者 Vladimir Burtman Haiyan Fu Michael S. Zhdanov 《Geomaterials》 2014年第4期117-128,共12页
Unconventional hydrocarbon reserves substantially surpass those of conventional resources and therefore are extremely economically attractive. However, exploration and production of uncon-ventional reserves is challen... Unconventional hydrocarbon reserves substantially surpass those of conventional resources and therefore are extremely economically attractive. However, exploration and production of uncon-ventional reserves is challenging. This paper demonstrates that one can observe significant induced polarization effects in shale reservoir rocks, which can be used in exploration for unconventional reserves. The generalized effective-medium theory of induced polarization (GEMTIP) was used to model the complex resistivity of shale rocks. We demonstrate that GEMTIP modeling provides an evaluation of mineral composition and volume fractions in rock samples. We have conducted spectral induced polarization (IP) measurements using different types of shale rocks to test the feasibility of the IP method and GEMTIP modeling for studying unconventional hydrocarbon (HC) reservoir rocks. 展开更多
关键词 UNCONVENTIONAL Energy RESOURCES EM EXPLORATION Induced polarIZATION effective MEDIUM
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POLAR SUBSTITUENT EFFECTS OF ORGANOPHOSPHORUS ESTERS IN STRUCTURE-REACTIVITY STUDIES 被引量:1
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作者 Wen Xiang HU Cheng Ye YUAN Shu Sen LI Shanghai Institute of Organic Chemistry,Chinese Academy of Sciences,345 Lingling Lu,Shanghai 200032 Institute of Pharmacology and Toxicology,Academy of Military Medical Sciences,Beijing 100850. 《Chinese Chemical Letters》 SCIE CAS CSCD 1992年第8期579-582,共4页
In order to study the polar substituent effect almost with no steric effect in organophosphorus chemistry,a series of 4-substituted-2,6,7-trioxa-1-phosphabicyclo[2.2.2]octane 1-oxides(1)and p-substituted phenylphospho... In order to study the polar substituent effect almost with no steric effect in organophosphorus chemistry,a series of 4-substituted-2,6,7-trioxa-1-phosphabicyclo[2.2.2]octane 1-oxides(1)and p-substituted phenylphosphonates(2)and corresponding mono hexyl esters(3)as model were synthesized.^(31)P-NMR chemical shifts of compounds(1)in methanol and deuterioacetone were determined.The Δδ values reflect 4-sbstituent po- lar effect.The ^(31)P-NMR of compounds(2)and(3)and the pKa of compounds(3)were also measured.The results showed that the trend of polar effects of substituents in both carboxylic and organophosphates chemistry are similar,and the change of polar effects in variation with the alkyl groups is not significant. 展开更多
关键词 MNDO polar SUBSTITUENT effectS OF ORGANOPHOSPHORUS ESTERS IN STRUCTURE-REACTIVITY STUDIES
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A two-dimensional fully analytical model with polarization effect for off-state channel potential and electric field distributions of GaN-based field-plated high electron mobility transistor
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作者 毛维 佘伟波 +11 位作者 杨翠 张超 张进成 马晓华 张金风 刘红侠 杨林安 张凯 赵胜雷 陈永和 郑雪峰 郝跃 《Chinese Physics B》 SCIE EI CAS CSCD 2014年第8期487-494,共8页
In this paper, we present a two-dimensional (2D) fully analytical model with consideration of polarization effect for the channel potential and electric field distributions of the gate field-plated high electron mob... In this paper, we present a two-dimensional (2D) fully analytical model with consideration of polarization effect for the channel potential and electric field distributions of the gate field-plated high electron mobility transistor (FP-HEMT) on the basis of 2D Poisson's solution. The dependences of the channel potential and electric field distributions on drain bias, polarization charge density, FP structure parameters, A1GaN/GaN material parameters, etc. are investigated. A simple and convenient approach to designing high breakdown voltage FP-HEMTs is also proposed. The validity of this model is demonstrated by comparison with the numerical simulations with Silvaco-Atlas. The method in this paper can be extended to the development of other analytical models for different device structures, such as MIS-HEMTs, multiple-FP HETMs, slant-FP HEMTs, etc. 展开更多
关键词 analytical model of GaN-based field-plated HEMT polarization effect POTENTIAL electric field
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Polarity Effects of Propylene Carbonate on Breakdown Strength in Microsecond Range
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作者 Zhen Wang Zi-cheng Zhang Jian-de Zhang 《Chinese Journal of Chemical Physics》 SCIE CAS CSCD 2015年第5期-,共4页
关键词 Breakdown strength Propylene carbonate polarity effect
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Influences of surface and flexoelectric polarization on the effective anchoring energy in nematic liquid crystal
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作者 关荣华 叶文江 邢红玉 《Chinese Physics B》 SCIE EI CAS CSCD 2015年第10期349-358,共10页
The physical effects on surface and flexoelectric polarization in a weak anchoring nematic liquid crystal cell are investigated systematically. We derive the analytic expressions of two effective anchoring energies fo... The physical effects on surface and flexoelectric polarization in a weak anchoring nematic liquid crystal cell are investigated systematically. We derive the analytic expressions of two effective anchoring energies for lower and upper substrates respectively as well as their effective anchoring strengths and corresponding tilt angles of effective easy direction.All of these quantities are relevant to the magnitudes of both two polarizations and the applied voltage U. Based on these expressions, the variations of effective anchoring strength and the tilt angle with the applied voltage are calculated for the fixed values of two polarizations. For an original weak anchoring hybrid aligned nematic cell, it may be equivalent to a planar cell for a small value of U and has a threshold voltage. The variation of reduced threshold voltage with reduced surface polarization strength is also calculated. The role of surface polarization is important without the adsorptive ions considered. 展开更多
关键词 surface and flexoelectric polarization effective anchoring energy easy direction hybrid aligned nematic threshold voltage
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High-Temperature Performance Analysis of AlGaN/GaN Polarization Doped Field Effect Transistors Based on the Quasi-Multi-Channel Model
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作者 房玉龙 冯志红 +6 位作者 李成明 宋旭波 尹甲运 周幸叶 王元刚 吕元杰 蔡树军 《Chinese Physics Letters》 SCIE CAS CSCD 2015年第3期117-120,共4页
We report on the temperature-dependent dc performance of A1GaN/GaN polarization doped field effect transistors (PolFETs). The rough decrements of drain current and transeonductance with the operation temperature are... We report on the temperature-dependent dc performance of A1GaN/GaN polarization doped field effect transistors (PolFETs). The rough decrements of drain current and transeonductance with the operation temperature are observed. Compared with the conventional HFETs, the drain current drop of the PolFET is smaller. The transeonductance drop of PolFETs at different gate biases shows different temperature dependences. From the aspect of the unique carrier behaviors of graded AlGaN/GaN heterostructure, we propose a quasi-multi-channel model to investigate the physics behind the temperature-dependent performance of AlGaN/GaN PolFETs. 展开更多
关键词 AlGaN High-Temperature Performance Analysis of AlGaN/GaN polarization Doped Field effect Transistors Based on the Quasi-Multi-Channel Model
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Mode decoupling in solid state ring laser based on stimulated Raman effect in polar crystals
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作者 罗章 袁晓东 +2 位作者 叶卫民 曾淳 季家镕 《Chinese Physics B》 SCIE EI CAS CSCD 2011年第2期255-259,共5页
In this paper we study the gain saturation induced mode-coupling control in solid state ring laser devices based on the stimulated Raman effect of the polar crystals in.order to realize solid state ring laser gyroscop... In this paper we study the gain saturation induced mode-coupling control in solid state ring laser devices based on the stimulated Raman effect of the polar crystals in.order to realize solid state ring laser gyroscopes. We theoretically investigate the mode coupling induced by gain saturation between clockwise (CW) and counterclockwise (CCW) propa- gating laser modes. Because the CW and CCW running waves are pumped with counter-propagating lasers respectively, the independent coexistence can be ensured. 展开更多
关键词 ring laser stimulated Raman effect polar crystals GYROSCOPE
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Determining the influence of ferroelectric polarization on electrical characteristics in organic ferroelectric field-effect transistors
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作者 浮宗元 张剑驰 +3 位作者 胡静航 蒋玉龙 丁士进 朱国栋 《Chinese Physics B》 SCIE EI CAS CSCD 2015年第5期597-605,共9页
Organic ferroelectric field-effect transistors (OFeFETs) are regarded as a promising technology for low-cost flexible memories. However, the electrical instability is still a critical obstacle, which limits the comm... Organic ferroelectric field-effect transistors (OFeFETs) are regarded as a promising technology for low-cost flexible memories. However, the electrical instability is still a critical obstacle, which limits the commercialization process. Based on already established models for polarization in ferroelectrics and charge transport in OFeFETs, simulation work is performed to determine the influence of polarization fatigue and ferroelectric switching transient on electrical characteristics in OFeFETs. The polarization fatigue results in the decrease of the on-state drain current and the memory window width and thus degrades the memory performance. The output measurements during the ferroelectric switching process show a hysteresis due to the instable polarization. In the on/off measurements, a large writing/erasing pulse frequency weakens the polarization modulation and thus results in a small separation between on- and off-state drain currents. According to the electrical properties of the ferroelectric layer, suggestions are given to obtain optimal electrical characterization for OFeFETs. 展开更多
关键词 organic ferroelectric field-effect transistors polarization fatigue ferroelectric switching
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Effects of Hydrogen-bonding Interaction and Polarity on Emission Spectrum of Naphthalene-Triethylamine in Mixed Solvent
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作者 Yoshimi Sueishi Shunzo Yamamoto 《Chemical Research in Chinese Universities》 SCIE CAS CSCD 2004年第5期606-611,共6页
The effects of the protic and aprotic polar solvents on the emission spectrum of the naphthalene-triethyl-amine system in THF were studied under conditions of steady-state illumination. The fluorescence spectrum of th... The effects of the protic and aprotic polar solvents on the emission spectrum of the naphthalene-triethyl-amine system in THF were studied under conditions of steady-state illumination. The fluorescence spectrum of the naphthalene-triethylamine system consists of two emission bands, the fluorescence band of naphthalene(band A, 329 nm) and the emission band of the exciplex(band B, 468 nm). The intensities of both the emission bands decrease with increasing the solvent polarity. The intensity of band B also decreases due to the hydrogen-bonding interaction between triethylamine and protic solvent, while that of band A increases. It is thus suggested that the quenching of naphthalene fluorescence by triethylamine in THF occurs through the charge transfer and electron transfer reactions. The spectral changes upon the increase of solvent polarity can be explained by the dependences of the equilibrium constant between exciplex and ion-pair and the rate constant for the electron transfer reaction from triethylamine to the excited naphthalene on the relative permittivity of solvent. It is shown that the formation of intermolecular hydrogen-bonding between triethylamine and protic solvent suppresses the quenching reaction by the decrease in free amine. Acetonitrile has only a polar effect and trichloroacetic acid only a hydrogen-bonding(or protonation) effect, while alcohols have both the effects. The effects of alcohols could be separated into the effects of solvent polarity and intermolecular hydrogen-bonding interaction quantitatively. 展开更多
关键词 Naphthalene-triethylamine Fluorescence spectrum Solvent effect Solvent polarity Hydrogen-bonding interaction.
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Influence of Isotope Effects on Product Polarizations of N(~2D)+D_2, N(~2D)+H_2 and N(~2D)+HD Reactive Systems
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作者 NIE Shan-shan CHU Tian-shu 《Chemical Research in Chinese Universities》 SCIE CAS CSCD 2012年第5期897-902,共6页
To figure out the influence of isotope effect on product polarizations of the N(2D)+D2 reactive system and its isotope variants, quasi-classical trajectory(QCT) calculation was performed on Ho's potential energy... To figure out the influence of isotope effect on product polarizations of the N(2D)+D2 reactive system and its isotope variants, quasi-classical trajectory(QCT) calculation was performed on Ho's potential energy surface(PES) of 2A″ state. Product polarizations such as product distributions of P(θr), P(φr) and P(θr,φr), as well as the generalized polarization-dependent differential cross sections(PDDCSs) were discussed and compared in detail among the four product channels of the title reactions. Both the intermolecular and intramolecular isotope effects were proved to be influential on product polarizations. 展开更多
关键词 Isotope effect Product polarization Quasi-classical trajectory calculation Potential energy surface
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Angular extent effect of micromotion target in SAR image by polar format algorithm 被引量:1
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作者 Bin Deng Yuliang Qin +1 位作者 Hongqiang Wang Yanpeng Li 《Journal of Systems Engineering and Electronics》 SCIE EI CSCD 2014年第3期428-433,共6页
Target micromotion not only plays an important role in target recognition but also leads to esoteric characteristics in synthetic aperture radar (SAR) imaging. This paper finds out an interesting phenomenon, i.e. th... Target micromotion not only plays an important role in target recognition but also leads to esoteric characteristics in synthetic aperture radar (SAR) imaging. This paper finds out an interesting phenomenon, i.e. the angular extent effect, in micro-motion target images formulated by the polar format algorithm. A micromotion target takes on multiple pairs of paired echoes (PEs) around the true point, and each PE extends for an angle which is exactly equal to the angular extent of the synthetic aperture, regardless of the micromotion frequency. The effect is derived and interpreted by using the characteristics of Bessel functions. Then it is demonstrated by simulation experiments of a target with different micromotion frequencies. The revelation and interpretation of the effect is highly beneficial to micromotion-target SAR image understanding as wel as target recognition. 展开更多
关键词 synthetic aperture radar (SAR) MICROMOTION MICRO-DOPPLER polar format algorithm (PFA) angular extent effect.
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Resolving multi-orbital effects on high harmonic generation from aligned N2 molecules in linearly and elliptically polarized intense laser fields
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作者 Hong-Jing Liang Xin Fan +6 位作者 Shuang Feng Li-Yu Shan Qing-Hua Gao Bo Yan Ri Ma Hai-Feng Xu Da-Jun Ding 《Chinese Physics B》 SCIE EI CAS CSCD 2019年第9期227-231,共5页
We perform an experimental study of the multi-orbital effect on the high-order harmonic generation(HHG) from aligned N_2 molecules in both linearly and elliptically polarized intense laser fields.Measured by a home-bu... We perform an experimental study of the multi-orbital effect on the high-order harmonic generation(HHG) from aligned N_2 molecules in both linearly and elliptically polarized intense laser fields.Measured by a home-built extreme ultraviolet(XUV) flat grating spectrometer with the pump-probe method, the angular distributions of different orders of HHG are obtained, which show distinctive behaviors for harmonics in the plateau and the cut-off regions.The ellipticity dependence of HHG is investigated by aligning the molecular axis parallel or perpendicular to the laser polarization.Our results indicate that both the highest occupied molecular orbital(HOMO) as well as the lower one(HOMO-1) contribute to the HHG of N2 molecules, in either linearly or elliptically polarized intense laser field.The study paves the way for understanding the ultrafast electron dynamics of molecules exposed to an intense laser field. 展开更多
关键词 high-order harmonic generation ALIGNED molecule multi-orbital effect elliptically polarIZED intense laser
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Optimal design of sub-wavelength metal rectangular gratings for polarizing beam splitter based on effective medium theory 被引量:3
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作者 赵华君 彭拥军 +3 位作者 谭菊 廖长荣 李鹏 任晓霞 《Chinese Physics B》 SCIE EI CAS CSCD 2009年第12期5326-5330,共5页
A novel optimal design of sub-wavelength metal rectangular gratings for the polarizing beam splitter (PBS) is proposed. The method is based on effective medium theory and the method of designing single layer antiref... A novel optimal design of sub-wavelength metal rectangular gratings for the polarizing beam splitter (PBS) is proposed. The method is based on effective medium theory and the method of designing single layer antireflection coating. The polarization performance of PBS is discussed by rigorous couple-wave analysis (RCWA) method at a wavelength of 1550 nm. The result shows that sub-wavelength metal rectangular grating is characterized by a high reflectivity, like metal films for TE polarization, and high transmissivity, like dielectric films for TM polarization. The optimal design accords well with the results simulated by RCWA method. 展开更多
关键词 polarizing beam splitter sub-wavelength metal rectangular gratings effective medium theory ANTIREFLECTION
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Nonlinear spectral cleaning effect in cross-polarized wave generation
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作者 Linpeng Yu Yi Xu +5 位作者 Fenxiang Wu Xiaojun Yang Zongxin Zhang Yuanfeng Wu Yuxin Leng Zhizhan Xu 《Chinese Physics B》 SCIE EI CAS CSCD 2018年第5期281-286,共6页
The underlying mechanism of the spectral cleaning effect of the cross-polarized wave(XPW) generation process was theoretically investigated. This study shows that the spectral noise of an input spectrum can be remov... The underlying mechanism of the spectral cleaning effect of the cross-polarized wave(XPW) generation process was theoretically investigated. This study shows that the spectral noise of an input spectrum can be removed in the XPW generation process and that the spectral cleaning effect depends on the characteristics of the input pulses, such as the chirp and Fourier-transform-limited duration of the initial pulse, and the modulation amplitude and frequency of the spectral noise. Though these factors codetermine the output spectrum of the XPW generation process, the spectral cleaning effect is mainly affected by the initial pulse chirp. The smoothing of the spectrum in the XPW generation process leads to a significant enhancement of the coherent contrast. 展开更多
关键词 nonlinear optics cross-polarized wave generation spectral cleaning effect
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Semiclassical investigation of Coulomb focusing effects in atomic above-threshold ionization with elliptically polarized laser fields
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作者 王传亮 夏立新 +1 位作者 姚洪斌 李文亮 《Chinese Physics B》 SCIE EI CAS CSCD 2017年第4期156-161,共6页
We investigate atomic above-threshold ionization in elliptically polarized strong laser fields with a semiclassical approach.With increasing laser intensity,the Coulomb focusing(CF) effects are found to become stron... We investigate atomic above-threshold ionization in elliptically polarized strong laser fields with a semiclassical approach.With increasing laser intensity,the Coulomb focusing(CF) effects are found to become stronger in both parallel and perpendicular directions with respect to the polarization plane.The dependence of CF effects on tunnel exit,initial transverse momentum distribution and laser electric field is analyzed.It was revealed that the effects of tunnel exit are most prominent with variation of the laser intensity,and the other two factors both play non-negligible roles.Our results provide a deeper insight to the recent experiments of Coulomb asymmetry[Shafir D,et al.,2013 Phys.Rev.Lett.111 023005 and Li M,et al,2013 Phys.Rev.Lett.111 023006]. 展开更多
关键词 above-threshold ionization Coulomb focusing effect semiclassical method elliptically polarized laser fields
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22MeV polarized proton scattering from ^(40)Ca and effective NN interactions
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作者 ANZHu CHENQuan 《Nuclear Science and Techniques》 SCIE CAS CSCD 2000年第3期187-191,共5页
Analyzing powers and differential cross sections have been measured for elastic scattering of 22MeV polarized protons from 40Ca, 16O and 12C, and differential cross sections for inelastic scattering of 22 MeV protons ... Analyzing powers and differential cross sections have been measured for elastic scattering of 22MeV polarized protons from 40Ca, 16O and 12C, and differential cross sections for inelastic scattering of 22 MeV protons from 3- (3.736 MeV) and 5-(4.491 MeV) states of 40Ca have also been measured. The experimental data for polarized proton elastic scattering have been analyzed with a phenomenological optical potential parameters, the experimental data and theoretical values are in good agreement. In the theoretical frame of microscopic single scattering model, transition densities extracted from electron inelastic scattering and M3Y and Halderson’s effective interactions have been utilized to analyze the experimental data of 22 MeV proton inelastic scattering from 40Ca. Overall, it seems that Halderson’s effective interaction can better describe the experimental data than M3Y although the degree of agreement between experimental and theoretical values needs to he improved. 展开更多
关键词 钙40 极化质子散射 核子-核子相应作用 弹性散射 原子核反应 实验研究
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Influence of the channel electric field distribution on the polarization Coulomb field scattering in In_(0.18) Al_(0.82) N/AlN/GaN heterostructure field-effect transistors
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作者 于英霞 林兆军 +4 位作者 栾崇彪 吕元杰 冯志红 杨铭 王玉堂 《Chinese Physics B》 SCIE EI CAS CSCD 2014年第4期517-520,共4页
By making use of the quasi-two-dimensional (quasi-2D) model, the current-voltage (l-V) characteristics of In0AsA10.82N/A1N/GaN heterostructure field-effect transistors (HFETs) with different gate lengths are sim... By making use of the quasi-two-dimensional (quasi-2D) model, the current-voltage (l-V) characteristics of In0AsA10.82N/A1N/GaN heterostructure field-effect transistors (HFETs) with different gate lengths are simulated based on the measured capacitance-voltage (C-V) characteristics and I-V characteristics. By analyzing the variation of the electron mobility for the two-dimensional electron gas (2DEG) with electric field, it is found that the different polarization charge distributions generated by the different channel electric field distributions can result in different polarization Coulomb field scatterings. The difference between the electron mobilities primarily caused by the polarization Coulomb field scatterings can reach up to 1522.9 cm2/V.s for the prepared In0.38AI0.82N/A1N/GaN HFETs. In addition, when the 2DEG sheet density is modulated by the drain-source bias, the electron mobility presents a peak with the variation of the 2DEG sheet density, the gate length is smaller, and the 2DEG sheet density corresponding to the peak point is higher. 展开更多
关键词 In0.18A10.82N/AIN/GaN heterostructure field-effect transistors channel electric field distribution polarization Coulomb field scattering two-dimensional electron gas mobility
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4′-N,N-二乙氨基-3-羟基苯并黄酮激发态分子内质子转移机制的溶剂极性效应——实验和理论研究
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作者 姜羊林 陈明卿 +4 位作者 梁民 尧奕歌 张燕 王鹏 张建平 《物理化学学报》 北大核心 2025年第2期116-124,共9页
激发态分子内质子转移(ESIPT)反应是一种重要的基础光化学反应,通常发生在具有分子内氢键的发色团中。3-羟基黄酮类衍生物(3-HFs)由于其广泛的天然来源和对环境极度敏感的荧光发光特性而备受关注。与3-HFs相比,4′-N,N-二乙氨基-3-羟基... 激发态分子内质子转移(ESIPT)反应是一种重要的基础光化学反应,通常发生在具有分子内氢键的发色团中。3-羟基黄酮类衍生物(3-HFs)由于其广泛的天然来源和对环境极度敏感的荧光发光特性而备受关注。与3-HFs相比,4′-N,N-二乙氨基-3-羟基黄酮(D-HBF)具有扩展的共轭体系和大幅红移的吸收特性,而最新研究表明,由于具有ESIPT特性,它可以用作环境极性敏感的生物荧光探针。本研究通过采用多种光谱和理论计算方法,系统研究了D-HBF在极性不同的三种非质子型溶剂(环己烷、乙醚和四氢呋喃)中的ESIPT反应机制。研究结果显示,在这三种溶剂中均能观测到D-HBF的ESIPT典型双发射峰,而这些峰的相对比率受溶剂极性的调控。荧光动力学分析揭示,随着溶剂极性的增加,激发态中正向和反向的质子转移反应速率都降低,同时反向质子转移变得更占优势。该研究还通过密度泛函理论和含时密度泛函理论计算,比较了三种溶剂中D-HBF的基态和激发态分子内氢键的键长和键角参数,确定了ESIPT反应是激发态分子内氢键增强机制。计算结果表明,增加溶剂极性会导致处于S1态的D-HBF分子的3-羟基伸缩振动红外吸收频率向高波数移动,这证明了相应的N^(*)态的分子内氢键减弱。此外,电子密度分析显示,引入在4′-位的强给电子官能团(4′-N,N-二乙氨基)使得D-HBF在激发态下具有典型的分子内电荷转移特征。最后,势能曲线计算结果表明,在激发态下质子转移更容易发生,而溶剂极性增加会导致更高的质子转移势垒,从而阻碍了相应的ESIPT反应。吉布斯自由能分析进一步表明,溶剂极性增加使激发态快速质子转移更倾向于向N^(*)态移动。这项研究为D-HBF类衍生物作为环境极性敏感的生物探针的应用提供了理论基础。 展开更多
关键词 4′-N N-二乙氨基-3-羟基苯并黄酮 激发态分子内质子转移 密度泛函理论/含时密度泛函理论 溶剂极性效应 荧光动力学
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