发光动力学

本文通过对辐射跃迁、无辐射跃迁和能量传递过程的讨论，介绍发光动力学的主要内容。     

打喷嚏动力学

正高速成像已经可以让研究者直接观察打喷嚏过程中液滴的形成机制。这项研究揭示了呼吸道猛烈地喷出液体后,在呼吸道之外爆裂成液滴的复杂变化过程,先从薄片状变成袋状,而后破碎成带状,最后成为液滴。研究组发现,剧烈的喷嚏使液滴在鼻子以外破碎得更小。这项研究对控制疾病的传播有重要意义,同     

质点动力学

从广义上看,质点动力学应包括惯性系内质点动力学和非惯性系内质点动力学;从研究方法上区分,还有用牛顿力学方法研究的质点动力学和用分析力学方法研究的质点动力学.这里所谓的质点动力学是狭义的,仅指在惯性系内用牛顿力学方法研究的质点动力学. 牛顿力学研究问题是采用分析和综合的方法、认为力学的研究对象──宏观物体(如刚体、弹性体、流体等)都是由有限个或无限个有着相互作用的质点组成的,搞清了其中最基本的元素──质点的运动规律,再将所有质点之间的相互作用和相互关联考虑进去,加以综合,就可以解决系统整体的运动问题.因此,质点…     

量子色动力学中的动力学自发破缺

本文用重整化群方程和Dyson方程研究了量子色动力学（QCD）中的动力学自发破缺问题.指出:（1）研究QCD中A类模型的动力学自发破缺这类非微扰问题时,电磁作用（和弱作用）的贡献是不能忽略的.（2）对许多实际模型（A类模型）来说,在QCD渐近自由时,对层子间的电磁作用做弱耦合近似的计算后,得到动力学自发破缺出现的结论.如果现在量子电动力学仍能用Johnson-Baker-Willey的自洽处理,或β_e有一紫外稳定固定点e_∞≠0（β_e的简单零点）且e_∞不太大,则上述结论在电磁作用的计算超出弱耦合近似时仍成立.     

量子系统的动力学对称性研究与代数动力学

文章介绍了量子系统的动力学对称性理论和代数动力学在人造了系统和量子光学系统中的应用。     

量子色动力学

量子色动力学(QCD)是一种尝试性强相互作用基本理论.在对强相互作用规律还没有完全认识的情况下,人们根据实验已经观测到的强相互作用性质以及寻找相互作用理论形式的一般原理——规范场论[1],提出了量子色动力学. 目前,虽然这个理论的物理结果还不完全清楚,可是许多物理学家却     

波包动力学-

本文介绍了波包动力学的基本理论和数值模拟方法,尤其是在飞秒激光与分子相互作用领域中的应用,探讨了飞秒激光引起的波包过程     

微液滴动力学特性的耗散粒子动力学模拟

对传统的耗散粒子动力学方法进行了改进.改进的耗散粒子动力学方法采用了包含远程吸引力和近距排斥力的保守力势函数,从而使得用耗散粒子动力学方法模拟多相流动成为可能.应用改进的耗散粒子动力学方法,对微尺度下液滴的形成及液滴在微重力下的大幅度振荡变形进行了数值模拟.计算结果表明,改进的耗散粒子动力学(DPD)方法能够有效地描述微尺度下液滴的动力学特性,对研究复杂流体多相流动有着重要的意义. 关键词： 多相流 微液滴 耗散粒子动力学(DPD)方法 保守力势函数     

分子马达动力学

分子马达是一类将化学能转化为机械能的微小机器. 对二维模型的研究表明, 非保守力在体系与外界能量交换中发挥重要作用. 四态模型较好地反映了马达力学化学过程的各个状态及相应的构象变化. Motor protein is a kind of small machines that convert chemical energy to mechanical works. It is revealed from the study of the two dimensional model that the non conservative impulsive force plays a significant role in the exchanging process of energy. A four state model characterizing the coupling of mechanical and chemical processes of molecular motor is also discussed.     

超快速反应动力学

十年前,《今日物理》发表了一期有关激光化学方面的文章,其中一篇强调了时间尺度在化学反应中的重要性以及用超短脉冲引发化学反应的可能性.十年来新的激光技术的出现以及气相分子束实验,揭示了基本化学反应各步骤.这些实验所揭示出的化学动力学过程的细节正是本篇文章的主题. 一般地从反应物到生成物的化学过程为 (1),(2)两式指出,有两种获得过渡态的办法:(1)过渡态产生于两个反应物间的碰撞,或称双分子反应2(2)过渡态是当一个稳定的分子获得了足够的能量,在碰撞的后半部分形成的生成物,因而也叫半碰撞反应或单分子反应.为了更好地了解化学…     

Exploring the oxidation chemistry of diisopropyl ether: Jet-stirred reactor experiments and kinetic modeling

Diisopropyl ether (DIPE) is considered as a promising gasoline additive due to the favorable blending Reid vapor pressure and the low water solubility. To get a good understanding of the DIPE oxidation chemistry, oxidation experiments of a stoichiometric mixture of DIPE/O₂/Ar/Kr were performed in a jet-stirred reactor (JSR) at atmospheric pressure over the temperature range of 525–900 K in this work. About 30 intermediates and products were identified and quantified using a photoionization molecular-beam mass spectrometer (PI-MBMS). Furthermore, a detailed kinetic model was proposed for DIPE oxidation, which showed satisfactory performances in predicting the species concentration profiles in this work as well as those in literature. For DIPE oxidation, the fuel consumption was observed only above 750 K, even though DIPE has two tertiary hydrogen atoms that are easy to be abstracted so that low-temperature oxidation reactivity is expected. The low oxidation reactivity at low temperature is because the formed OOQOOH radical mostly dissociates back to QOOH+O₂, instead of undergoing intramolecular isomerization which leads to the low-temperature chain-branching. At higher temperature, DIPE is mainly consumed by hydrogen abstraction reactions from the carbon atoms adjacent to the oxygen atom, producing dominantly the IC₃H₇OC(CH₃)₂ fuel radical, which then decomposes rapidly via CO bond β-scission instead of combining with O₂. In contrast, the minor fuel radical IC₃H₇OCH(CH₃)CH₂ tends to go through the O₂ addition reaction and the subsequent chain branching reactions, as confirmed by the detection of cyclic ether intermediates. Propylene and acetone are the most abundant intermediates in DIPE oxidation, both of which predominantly come from the initial fuel decomposition steps. Other intermediates are mainly formed via the consumption of these two species.     

Exploring the low-temperature oxidation chemistry of 1-butene and i-butene triggered by dimethyl ether

In order to better understand the low-temperature oxidation chemistry of alkenes, 1-butene and i-butene oxidation experiments triggered by dimethyl ether (DME) were conducted in a jet-stirred reactor at 790 Torr, 500–725 K and the equivalence ratio of 0.35. Low-temperature oxidation intermediates involved in alcoholic radical chemistry and allylic radical chemistry were detected by using synchrotron vacuum ultraviolet photoionization mass spectrometry (SVUV-PIMS). To better interpret the experimental data, a kinetic model was proposed based on our low-temperature oxidation model of DME and comprehensive oxidation models of 1-butene and i-butene in literature. Based on present experimental results and modeling analysis, alcoholic radical chemistry initiated by OH addition is mainly responsible for the low-temperature chain propagation of butenes, since the Waddington mechanism plays a dominant role compared with the chain-branching pathways through the second O₂ addition. Allylic radical+HO₂ reactions producing alkenyl hydroperoxides and fuel+O₂ serve as the major chain-branching and chain-termination pathways, respectively, and they are competitive in the negative temperature coefficient (NTC) region. In contrast, chain-branching pathways originating from allylic radical+O₂ and alkyl-like radical+O₂ reactions have little contribution to the OH formation. Comparison with the simulation results of butane/DME mixtures demonstrates that butenes can largely inhibit the reactivity of DME at low temperatures due to its reduced low-temperature chain-branching process. However, in the NTC region, butenes may not be good OH absorbents since the allylic radicals can convert HO₂ to OH and consequently enhance the oxidation reactivity.     

Low-temperature combustion chemistry of biofuels: Pathways in the low-temperature (550–700 K) oxidation chemistry of isobutanol and tert-butanol

Butanol isomers are promising next-generation biofuels. Their use in internal combustion applications, especially those relying on low-temperature autoignition, requires an understanding of their low-temperature combustion chemistry. Whereas the high-temperature oxidation chemistry of all four butanol isomers has been the subject of substantial experimental and theoretical efforts, their low-temperature oxidation chemistry remains underexplored. In this work we report an experimental study on the fundamental low-temperature oxidation chemistry of two butanol isomers, tert-butanol and isobutanol, in low-pressure (4–5.1 Torr) experiments at 550 and 700 K. We use pulsed-photolytic chlorine atom initiation to generate hydroxyalkyl radicals derived from tert-butanol and isobutanol, and probe the chemistry of these radicals in the presence of an excess of O₂ by multiplexed time-resolved tunable synchrotron photoionization mass spectrometry. Isomer-resolved yields of stable products are determined, providing insight into the chemistry of the different hydroxyalkyl radicals. In isobutanol oxidation, we find that the reaction of the α-hydroxyalkyl radical with O₂ is predominantly linked to chain-terminating formation of HO₂. The Waddington mechanism, associated with chain-propagating formation of OH, is the main product channel in the reactions of O₂ with β-hydroxyalkyl radicals derived from both tert-butanol and isobutanol. In the tert-butanol case, direct HO₂ elimination is not possible in the β-hydroxyalkyl + O₂ reaction because of the absence of a beta C–H bond; this channel is available in the β-hydroxyalkyl + O₂ reaction for isobutanol, but we find that it is strongly suppressed. Observed evolution of the main products from 550 to 700 K can be qualitatively explained by an increasing role of hydroxyalkyl radical decomposition at 700 K.     

Vibrational non-equilibrium in the hydrogen–oxygen reaction. Comparison with experiment

A theoretical model is proposed for the chemical and vibrational kinetics of hydrogen oxidation based on consistent accounting of the vibrational non-equilibrium of the HO₂ radical that forms as a result of the bimolecular recombination H+O₂ → HO₂. In the proposed model, the chain branching H+O₂ = O+OH and inhibiting H+O₂+M = HO₂+M formal reactions are treated (in the terms of elementary processes) as a single multi-channel process of forming, intramolecular energy redistribution between modes, relaxation, and unimolecular decay of the comparatively long-lived vibrationally excited HO₂ radical, which is able to react and exchange energy with the other components of the mixture. The model takes into account the vibrational non-equilibrium of the starting (primary) H₂ and O₂ molecules, as well as the most important molecular intermediates HO₂, OH, O₂(¹Δ), and the main reaction product H₂O. It is shown that the hydrogen–oxygen reaction proceeds in the absence of vibrational equilibrium, and the vibrationally excited HO₂(v) radical acts as a key intermediate in a fundamentally important chain branching process and in the generation of electronically excited species O₂(¹Δ), O(¹D), and OH(²Σ⁺). The calculated results are compared with the shock tube experimental data for strongly diluted H₂–O₂ mixtures at 1000 < T < 2500 K, 0.5 < p < 4 atm. It is demonstrated that this approach is promising from the standpoint of reconciling the predictions of the theoretical model with experimental data obtained by different authors for various compositions and conditions using different methods. For T < 1500 K, the nature of the hydrogen–oxygen reaction is especially non-equilibrium, and the vibrational non-equilibrium of the HO₂ radical is the essence of this process. The quantitative estimation of the vibrational relaxation characteristic time of the HO₂ radical in its collisions with H₂ molecules has been obtained as a result of the comparison of different experimental data on induction time measurements with the relevant calculations.     

Pathway exploration in low-temperature oxidation of a new-generation bio-hybrid fuel 1,3-dioxane

The joint and flexible utilization of renewable electricity, ligno-cellulosic biomass, and/or CO₂ point sources to produce so-called bio-hybrid fuels is a promising solution to achieve carbon neutrality while still meeting the energy demand of the transportation sector. One of the new-generation bio-hybrid fuels is 1,3-dioxane. It has a special chemical structure with two oxygen atoms in a six-membered ring. In this work, the low-temperature oxidation of 1,3-dioxane was studied theoretically and experimentally. Potential energy surfaces of the products of the O₂ recombination with the three radicals formed from the H-atom abstraction of 1,3-dioxane were calculated at the DLPNO-CCSD(T)/CBS//B2PLYP-D3/cc-pVTZ level. The reaction rate coefficients were calculated with the RRKM/master equation method (T = 500–2000 K, p = 0.01–100 atm). To validate the proposed pathways, low-temperature oxidation experiments of 1,3-dioxane were performed in a jet stirred reactor (JSR) coupled with a synchrotron photon ionization time of flight molecular beam mass spectrometer (T = 590 K, p = 1 bar). Key intermediates in the investigated pathways were captured and identified by the combination of measured photon ionization efficiency curves and calculated ionization energies. Compared to cyclohexane, which has no oxygen in the six-membered ring, 1,3-dioxane has much weaker C-H bonds for the carbon between the two oxygen atoms, thus enabling faster internal H-atom migration from ROO to QOOH. Furthermore, oxidation of 1,3-dioxane tends to favor cyclic ethers + OH (chain propagation) instead of alkenes + HO₂ (chain termination), explaining its high reactivity in the low-temperature regime.     

Effect of γ-irradiation and semiconducting oxide (tio2) on the thermal decomposition of mgc2o4: A comparative study

The simultaneous rising temperature (DTA-TG) technique and the gas evolution method are adopted for studying the thermal decomposition of unirradiated and irradiated MgC₂O₄ and MgC₂O₄ + TiO₂ mixtures. The data are applied to theories of different solid state reaction models and the best fit is obtained for the Avrami-Erofeev mechanism (n=2) suggesting that both the nucleation and growth processes occur at the reactant product interface in a two dimensional chain branching manner. Low irradiation doses decrease the rate of reaction remarkably whereas the reverse phenomenon takes place at higher doses. The n-type semiconducting oxide, TiO₂ (5-40 mol%) enhances the rate of decomposition which increases with increasing concentration of the catalyst. The influence of n -irradiation is explained in the light of defects, dislocations and electron-hole (e^?, h⁺) pairs generated in the lattice, whereas the influence of TiO₂ is understood on the basis of electron transfer process involved in the reaction.     

O− emission from 12CaO·7Al2O3 and MSZ composite and its application for silicon oxidation

The solid electrolyte 12CaO·7Al₂O₃ (C12A7) is an interesting material where an atomic oxygen radical anion (O⁻) can be emitted from the C12A7 to vacuum when it is heated to 1000 K under an applied electric field (100 V/cm). However, the mechanical strength of the C12A7 is not enough for an application study. In order to enhance the mechanical strength of the C12A7, a magnesia-stabilized zirconia (MSZ) support C12A7 film composite was developed, and ion emission from the MSZ/C12A7 composite was investigated. The MSZ/C12A7 composite showed O⁻ emission and also electron emission. The generated O⁻ was applied to a silicon sample to confirm its oxidation ability. Even though the surface temperature is less than 383 K, SiO₂ film formation was achieved.This O⁻ oxidation method is applicable for low-temperature and low-damage silicon oxidation processes.     

Probing the low-temperature chemistry of methyl hexanoate: Insights from oxygenate intermediates

Understanding the combustion of methyl esters is crucial to elucidate kinetic pathways and predict combustion parameters, soot yields, and fuel performance of biodiesel, however most kinetic studies of methyl esters have focused on smaller, surrogate model esters. Methyl hexanoate is a larger methyl ester approaching the chain length of methyl esters found in biodiesel and has not received as much research attention as other smaller esters. The purpose of this work is to present the first atmospheric pressure combustion data of methyl hexanoate, CH₃CH₂CH₂CH₂CH₂COOCH₃. Mixtures of 2% methyl hexanoate in O₂ and N₂ are studied using a plug flow reactor at atmospheric pressure, wall temperatures from 573 to 973 K, residence times from roughly 1-2 s., and fuel equivalence ratios of 1, 1.5, and 2. Exhaust gases are analyzed by a gas chromatograph-mass spectrometer system and species mole fractions are presented. The literature model shows satisfactory agreement with the experimental species profiles and improvements for future mechanistic studies are suggested. In particular, this work proposes new unimolecular decomposition pathways of methyl hexanoate to form methanol or methyl acetate. Furthermore, the experiment detected three unsaturated esters that are direct products of the low temperature oxidation chemistry and it provides more insight into branching ratios for the formation of methyl hexanoate radicals and for the decomposition of hydroperoxyalkyl radicals.     

Phase relations in the Fe-P system at high pressures and temperatures from ab initio computations

ABSTRACT

Based on the first-principles calculations within the density functional theory and crystal structure prediction algorithms iron phosphide phases stable under pressure of the Earth’s core and temperatures up to 4000?K were determined. A new low-temperature modification FeP-P2₁/c stable above ～75?GPa was predicted. Fe₂P with the allabogdanite structure has been established to be stable in the low-temperature region at ambient conditions. At 750?K it transforms into the barringerite structure. The transition from Fe₃P with schreibersite structure to Fe₃P-Cmcm was observed at 27?GPa, and the phase transition boundary is nearly isobaric. Fe₂P and FeP are thermodynamically stable at the Earth’s inner core pressures and 0?K according to the obtained results, whereas Fe₃P stabilizes with respect to decomposition to Fe?+?Fe₂P at high temperatures above ～3200?K.     

Atmospheric chemistry of HFE-7000 (i-C3F7OCH3) and isofluoro-propyl formate (i-C3F7OC(O)H): reactions with OH radicals,atmospheric lifetime and fate of alkoxy radical (i-C3F7OCH2O•) – a DFT study

ABSTRACT

The mechanism of hydrogen abstraction reaction between HFE-7000 (i-C₃F₇OCH₃) and OH radicals using M06-2X functional in conjunction with 6-31+G(d,p) basis set is investigated. The pre-reactive and post-reactive complexes from intrinsic reaction coordinate calculations are validated at entrance and exit channels, respectively. The standard enthalpies of formation for the species and bond dissociation energy for C–H bond are also estimated. The rate constants of the titled reactions over the temperature range of 250–450 K are reported. The OH-driven atmospheric life time of i-HFE-7000 is computed to be 3.19 years. The atmospheric fate of the alkoxy radical (i-C₃F₇OCH₂O^?) is also explored here for the first time. Three prominent plausible decomposition channels including oxidation are considered in detail. The thermochemical data reveal that reaction with O₂ is the dominant path for the decomposition of i-C₃F₇OCH₂O^? radical. Moreover, rate constant for the OH-initiated hydrogen abstraction of isofluoro-propyl formate (i-C₃F₇OC(O)H) is also reported.