高电荷态离子引起的富勒烯离子的碎裂

离子在与富勒烯的相互作用过程中会导致C60分子的激发。处于低激发态的C60r 离子通过发射中性C2分子或带电的轻团簇碎片Cn 等非对称碎裂方式来耗散激发能,但如果激发能很高,笼形的C60r 离子可能会彻底崩溃,而发生多重碎裂。C60r 离子的碎裂过程与其电荷态r及分裂势垒密切相关。低电荷态的C60r (r≤3)离子蒸发一个C2分子需要克服10.3 eV左右的势垒。随着电荷态的升高,发射带电的Cn 会变得越来越容易,并逐渐过渡到多重碎裂过程。另一方面,C60r 离子的碎裂机制还与激发方式有关,在直接正碰过程中,将C60分子当作固体薄靶来处理,通过分析不同价态的C60r 离子的碎片谱,发现母核的初始电荷态决定碎裂方式,由此获得一个可以表征激发能大小的可观测量——发射电子个数。     

高电荷态离子引起的富勒烯离子的碎裂

离子在与富勒烯的相互作用过程中会导致C60分子的激发。处于低激发态的C60r+离子通过发射中性C2分子或带电的轻团簇碎片Cn+等非对称碎裂方式来耗散激发能,但如果激发能很高,笼形的C60r+离子可能会彻底崩溃,而发生多重碎裂。C60r+离子的碎裂过程与其电荷态r及分裂势垒密切相关。低电荷态的C60r+(r≤3)离子蒸发一个C2分子需要克服10.3 eV左右的势垒。随着电荷态的升高,发射带电的Cn+会变得越来越容易,并逐渐过渡到多重碎裂过程。另一方面,C60r+离子的碎裂机制还与激发方式有关,在直接正碰过程中,将C60分子当作固体薄靶来处理,通过分析不同价态的C60r+离子的碎片谱,发现母核的初始电荷态决定碎裂方式,由此获得一个可以表征激发能大小的可观测量——发射电子个数。     

纳秒激光诱导C60分子碎裂中轻碎片离子C+n(n《30)的产生机理研究

采用飞行时间质谱计测量了纳秒激光诱导C60分子碎裂中轻碎片离子C n(n≤11)的初始平均动能,结果显示轻碎片离子具有相同的初始平均动能(约为0.34 eV),并且该动能在一定范围内不随激光通量的变化而明显改变.结合前人的实验结果,对纳秒激光诱导C60分子碎裂中轻碎片离子C n(n<30)的主要产生模式作了新的阐述,即C60分子级联发射15个C2分子和一个电子形成自身不稳定的C 30离子,在皮秒时间尺度内C 30离子的笼形结构塌陷,进而轻碎片离子产生.     

乙胺分子的多光子电离过程质谱研究

报道了乙胺分子在４４０～４７５ｎｍ波长范围内多光子电离（ＭＰＩ）质谱（ＭＳ）研究结果。碎片离子主要由母体离子碎裂模式产生。母体离子ＣＨ３ＣＨ２Ｎ＋·Ｈ２由经３ｓ里德堡态的（２＋２）共振多光子电离产生后，大部分发生β键断裂，形成ＣＨ２＝Ｎ＋Ｈ２离子，还有一部分再吸收一个光子，通过Ｃ－Ｈ（ＣＨ２）键的断裂产生了ＣＨ３ＣＨ＝Ｎ＋Ｈ２离子。ＣＨ３ＣＨ＝Ｎ＋Ｈ２和ＣＨ２＝Ｎ＋Ｈ２离子最容易发生的碎裂过程是脱去氢分子，分别产生Ｃ２Ｈ４Ｎ＋（分子式）离子和ＣＨ≡Ｎ＋Ｈ离子。     

乙胺分子的多光子电主过程质谱研究

报道了乙胺分子在４４０－４７５ｎｍ波长范围内多光子电离（ＭＰＩ）质谱（ＭＳ）研究结果。碎片离子主要由母体离子碎裂模式产生。母体离子ＣＨ３ＣＨ２ＮＨ２由经３ｓ里德堡态的（２＋２）共振多光子电离产生后，大部分发生β键断裂，形成ＣＨ２＝Ｎ＋Ｈ２离离子，还有一部分再吸收一个光子，通过Ｃ－Ｈ（ＣＨ２）键的断裂产生了ＣＨ３ＣＨ－ＮＨ２离子。ＣＨ３ＣＨ＝ＮＨ２和ＣＨ２＝ＮＨ２离子最容易发生的碎裂过程是脱去氢分子     

30MeV/u~(40)Ar ~(159)Tb反应中中等质量碎片的发射时标与发射机制

报道３０ＭｅＶ／ｕ４０Ａｒ＋１５９Ｔｂ反应中碎片碎片关联函数的实验结果．利用三体弹道模型从关联函数提取了中等质量碎片发射时间．中等质量碎片的平均发射时间随碎片能量而变化，从低能时的约５００ｆｍ／ｃ下降至高能时的约１００ｆｍ／ｃ．中等质量碎片发射时间随束流能量的升高而下降，表明随着束流能量的升高中等质量碎片发射机制逐渐从相继两体衰变向多重碎裂发射过渡．对于４０Ａｒ＋１５９Ｔｂ反应，此过渡能区在３５—４５ＭｅＶ／ｕ之间     

264～280nm波段萘的共振增强多光子电离研究

在我们自己研制的具有恒温加热进样系统的激光质谱仪上实验获得了气相萘分子的共振增强多光子电离广色行时问质谱（REMPI—TOFMS），以及萘母体离子C10Hg8^＋和一些主要碎片离子C8Hg6^＋、C6Hg6^＋、C5H3^＋、C4Hg3^＋、C3Hg3^＋在264～280nm、的分质量光谱，结合在266nm 激发波长下实验得到的这些离子的光强指数及不同激光能量下的分支比，对母体离子及主要碎片离子的生成机理进行了探讨：在试波段范围内，萘母体分子首先吸收一个光子从基态跃迁至激发态，激发态分子再吸收一个光子而电高产生母体离子C10Hg8^＋时；碎片离子C8Hg6^＋、C6Hg6^＋、C5Hg3^＋、C4Hg3^＋、C3Hg3^＋则是由母体离子进一步吸收光子解离形成的，并给出了可能的解离通道。     

中能原子核多重碎裂中的方位角关联

在发射源静止系碎片各向同性发射的假设条件下，考虑到碎片之间的电磁作用，研究了中能原子核多重碎裂中碎片间的方位角关联，计算结果与５００─９８０ＡＭｅＶ能区的实验数据一致．     

266nm下邻二甲苯双光子电离质谱的研究

利用YAG激光器输出的四倍频激光对邻二甲苯分子的多光子电离过程进行了研究,获得了邻二甲苯分子的多光子电离飞行时间质谱（MPI-TOFMS）,其母体离子及碎片离子信号达22种之多。光强指数分析表明母体离子C8H^＋10和主要的碎片离子C7H^＋7、C6H^＋5发生了1＋1共振增强双光子电离（RE2MPI）。     

高电荷态离子Arq+与不同金属靶作用产生的X射线

研究了高电荷态离子Ar^q+(q=16，17，18)入射金属Be，Al，Ni，Mo，Au靶表面产生的X射线谱.实验结果表明，Ar的Kα-X射线是离子在与固体表面相互作用过程中固体表面之下形成空心原子发射的.电子组态1s²的高电荷态Ar¹⁶⁺离子在金属表面中性化过程中，存在的多电子激发过程使Ar¹⁶⁺的K壳层电子激发产生空穴，级联退激发射Ar的Kα 特征X射线.Ar¹⁷⁺离子在金属表面作用过程中产生的X射线谱形与靶材料没有明显的关联,入射离子的Kα-X射线产额与其最初的电子组态有关，靶原子的X射线产额与入射离子的动能有关. 关键词： 高电荷态离子 空心原子 多电子激发 X射线     

化学位移试剂用于均四嗪衍生物的13C核磁共振谱研究

本文用位移试剂Pr(fod)₃和Eu(fod)₃研究了均四嗪衍生物的¹³C-NMR波谱。它们之间的配位能力与均四嗪环上的电子云密度有关。通过诱导位移值,确定环上两个碳原子的化学位移值在163-171PPm范围内。探讨了诱导位移的机制,对Pr(fod)₃,以伪接触机制为主,而对Eu(fod)₃,接触机制有重要贡献。     

偏心滑轮间歇输片机构的改进

将双偏心滑轮间歇片机构的一个滑轮,改成偏心半径仅为主滑轮的1/m,并以两倍的速度旋转,可以有效地改善偏心滑轮机构的间歇输片特性。     

Generalized entropy production analysis for mechanism reduction

The paper introduces a generalized formulation for the computation of the relative contribution of each elementary reaction to the total entropy production, which has been proposed as a measure of the importance of elementary reactions and used for the reduction of detailed chemical reaction mechanisms. The reduction method is extended for the cases where the principle of detailed balance does not hold or apply, namely in the case of irreversible reactions or when the reverse rate constants are not computed via the thermodynamic equilibrium constants. Using a mechanism for n-butane consisting exclusively of reversible reactions, the new formulation is compared to the original one, and then applied for the construction of a skeletal mechanism for n-dodecane starting from a detailed mechanism which includes predominantly irreversible reactions. The skeletal scheme is found to accurately capture the ignition delay times over an extended range of pressure, initial temperature and equivalence ratio, the steady-state temperature as function of the residence time in a non-isothermal adiabatic perfectly stirred reactor, and the laminar flame speed of atmospheric flames at different unburned mixture temperatures and equivalence ratios.     

Theoretical study on the Cope rearrangement mechanisms and the homoaromaticity of semibullvalene,barbaralane, and 1,5‐methanosemibullvalene

Cope rearrangement mechanisms and the homoaromaticity of semibullvalene, barbaralane, and 1,5‐methanosemibullvalene in the ground and lowest excited states were studied by ab initio methods. In the ground state, the rearrangement reactions of semibullvalene and barbaralane occurred concertedly through the transition states with C_2v symmetry, and the transition states had a homoaromatic nature. In particular, the transition state of barbaralane exhibited the strongest homoaromaticity among the three systems treated here. On the other hand, for 7,8‐methanosemibullvalene, the structure with C_2v symmetry was not a transition state but one with a stable energy minimum. The energy minimum structure with C_2v symmetry had a biradical character. The lowest excited states of semibullvalene and barbaralane were the excitation to the σ* anti‐orbital, ¹B₂ and ¹B₁ states, and led to near di‐allyl states. The lowest excitation state of 1,5‐methanosemibullvalene had C_s symmetry and was the A″ state excitation in one side of two allyl parts. Copyright © 2011 John Wiley & Sons, Ltd.     

高频语抗噪声通讯系统的语言可懂度实验研究

通过对高频语抗噪声通讯系统的研究，并经实验证明该系统的高频语通讯具有很强的抗环境噪声功能，较好地解决了噪声环境中的传递语音，高频语生成的数学表达。高频语通讯装置的研究设计；采用该装置在实验室内分别用语音声级85、90，95dB(A)在高于该声级的噪声环境下作或懂度实验研究；高频语声级90dB（A)在舰船主机舱室105dB(A)环境下载与不载耳塞的可懂度试验，该系统的形成，在语音，环境噪声比为－10至－15dB时语言可懂度可达90％以上，从理论上升到研制装置成功，突破了传统的语言传递遵循部位机理的信噪比必须为＋5dB的论点。     

Mechanical passive and active models of the human basilar membrane

Simple three-dimensional passive and active models of the human basilar membrane were built, solved using the Finite Element Method and tested. In the active model an active mechanism connected with electromotility of outer hair cells was included. In the active model the active mechanism was incorporated in the form of additional, local pressure load. In the passive model the active mechanism was neglected. Hydrodynamic coupling between the cochlear partition and cochlear fluid was excluded in both models. Geometrical and physical parameters of the model were chosen to be adequate to those of humans in the best possible way. However, some of these parameters had to be estimated. The models were tested by calculation of typical curves known from cochlear measurements performed mostly on animals. For the passive model a linear input-output function and very small values of the basilar membrane velocities were obtained. This behaviour is to be expected for the passive model and for the basilar membrane in the poor physiological condition. For the active model the compressed input-output functions, tuning curves, isointensity curves and reasonable BM velocities were obtained. Possible inadequacies, which could explain the differences between numerical results and measurements were described.     

A skeletal mechanism for flame inhibition by trimethylphosphate

On the basis of a multi-step kinetic mechanism for flame inhibition by organophosphorus compounds including more than 200 reactions, a skeletal mechanism for flame inhibition by trimethylphosphate was developed. The mechanism consists of 22 irreversible elementary reactions, involving nine phosphorus-containing species. Selection of the crucial steps was performed by analysing P-element fluxes from species to species and by calculating net reaction rates of phosphorus-involving reactions versus the flames zone. The developed mechanism was validated by comparing the modelling results with the measured and simulated (using the starting initial mechanism) speed and the chemical structure of H₂/O₂, CH₄/O₂ and syngas/air flames doped with trimethylphosphate. The mechanism was shown to satisfactorily predict the speed of H₂/O₂/N₂ flames with various dilution ratios, CH₄/air and syngas/air flames doped with trimethylphosphate. The skeletal mechanism was also shown to satisfactorily predict the spatial variation of H and OH radicals and the final phosphorus-containing products of the inhibitor combustion. Further reduction of the skeletal mechanism without modification of the rate constants recommended in the starting mechanism was shown to result in noticeable disagreement of the flame speed and structure.     

ZnO纳米线的合成与生长机理

采用化学气相沉积系统制备ZnO纳米线,以覆盖一层约5nm厚的Ag薄膜的单晶Si(001)为衬底,纳米线的生长遵循气-液-固(VLS)机理。对得到的样品采用X射线衍射(XRD)和扫描电镜(SEM)进行晶体结构和形貌的表征。XRD结果表明衬底温度在600~700℃时生长的ZnO纳米线具有六方结构和统一的取向。通过扫描电子显微镜分析,比较了生长温度对纳米线直径和长度的影响。实验表明我们可以通过催化剂和温度来实现ZnO纳米线生长的可控。与传统的VLS生长方式不同的是在我们制备的ZnO纳米线顶端并没有看到催化剂颗粒,表明纳米线的生长方式是底部生长,我们对其生长机理进行了研究。     

Criteria for selection of components for surrogates of natural gas and transportation fuels

The present paper addressed the production of soot precursors, acetylene, benzene and higher aromatics, by the paraffinic (n-, iso-, and cyclo-) and aromatic components in fuels. To this end, a normal heptane mechanism compiled from sub-models in the literature was extended to large normal-, iso-, and cyclo-paraffins by assigning generic rates to reactions involving paraffins, olefins, and alkyl radicals in the same reaction class. Lumping was used to develop other semi-detailed sub-models. The resulting mechanism for components of complex fuels (named the Utah Surrogate Mechanism) includes detailed sub-models of n-butane, n-hexane, n-heptane, n-decane, n-dodecane, n-tetradecane and n-hexadecane, and semi-detailed sub-models of i-butane, i-pentane, n-pentane, 2,4-dimethyl pentane, i-octane, 2,2,3,3-tetramethyl butane, cyclohexane, methyl cyclohexane, tetralin, 2-methyl 1-butene, 3-methyl 2-pentene and aromatics. Generic rates of reaction classes were found adequate to generate reaction mechanisms of large paraffinic components. The predicted maximum concentrations of the fuel, oxidizer, and inert species, major products and important combustion intermediates, which include critical radicals and soot precursors, were in good agreement with the experimental data of three premixed flames of composite fuels under various conditions. The relative importance in benzene formation of each component in the kerosene surrogate was found to follow the trend aromatics > cyclo-paraffins > iso-paraffins > normal-paraffins. In contrast, acetylene formation is not that sensitive to the fuel chemical structure. Therefore, in formulation of surrogate fuels, attention should be focused on selecting components that will yield benzene concentrations comparable to those produced by the fuel, with the assurance that the acetylene concentration will also be well approximated.