正戊烷与SO2气相光化学反应自由基机理的ESR验证

烷烃与SO2的气相光化学作用为自由基反应[1].Penzhorn等[2]对C4以下的气相烷烃与SO2光化学反应产物的复杂性和多样性进行了推测,此后对该光化学反应机理的研究均以反应产物(特别是凝聚态产物)为基础进行的[3].为验证烷烃与SO2光化学反应体系中确实存在自由基,Makarov等[4]向正戊烷与SOz光化学反应体系中引入NO,通过对反应起始阶段的产物的光谱分析和反应动力学研究,论证了该反应的自由基过程.ESR技术是检测自由基的有效方法,Stokes等[5]利用自旋捕集-ESR技术成功地测得了气相羟基自由基的存在.     

氨基羧酸铁(III)配合物催化分解过氧化氢

用碘量法研究了[Fe（EDTA],[FeⅢ(DCTA)],[FeⅢ(EGTA)]催化分解H2O2反应，提出了反应动力学方程为-d[H2O2]/dt=k[FE(Ⅲ)][H2O2][H ]^-1，认为氨基羧酸铁（Ⅲ）配合物催化分解H2O2反应为键式自由基反应，反应中间体包括过氧铁（Ⅲ）配合物，氨基羧酸铁（Ⅱ）和HO-，HO2-自由基。     

新型含磷酰基的脂溶性自由基捕捉剂的合成及其ESR研究

超氧阴离子自由基的研究最近得到了广泛的关注 ,这主要是因为超氧阴离子自由基及由其诱导产生的各种活性氧 ( HOO· ,HO· 和 H2 O2 )与许多病理过程有关 ,如发炎 [1] 、缺血再灌综合症 [2 ] 、 DNA损伤[3] 和神经死亡疾病 [4 ] 等 .自旋捕捉技术是检测自由基最有效的方法 [5～ 9] ,近年来在生物体系活性氧自由基检测中得到广泛应用 [10 ,11] ,大力推动了生物自由基领域的研究 .合成新型自由基捕捉剂及改善其对超氧阴离子自由基的捕捉性能一直是人们追逐的热点 ,我们正致力于这方面的研究 [12 ] .其中提高自由基捕捉剂的脂溶性 ,扩大自…     

N2O分解反应的动力学-Monte Carlo模拟

N2O是一种大气污染物，许多金属氧化物能使它发生分解反应，生成N2和O2．因此，N2O的催化分解反应很早就引起了研究者的兴趣[1]．传统的动力学着重去研究反应速率和一些反应参数，如温度、压力、组成等的关系，往往忽视催化表面的性质，从而使速率方程变得十分复杂．Kobayashi等人利用过渡应答法研究了N2O分解反应的动力学，计算了两个基元步骤的速率常数，但没有给出表面物种浓度变化的更进一步的信息[2]．近年来，MonteCarlo方法在研究表面反应机理和动力学方面已经取得了一些成功[3，4]．我们曾用MonteCarlo方法研究了N2O催化分解…     

5,6-苯并-2-亚甲基-1,3-二氧环庚烷的活性自由基开环聚合反应

活性 (或称可控 )自由基聚合研究是目前高分子科学的研究热点之一[1～ 8] .活性自由基聚合制备的聚合物具有分子量随转化率提高而线性增加、分子量分布窄和聚合反应为一级反应动力学等特点 .自由基开环聚合所得产物体积收缩小 ,某些含有不饱和双键的螺环单体发生双开环聚合时甚至发生体积膨胀 ;开环聚合还可在聚合物主链上引入各种官能团 ,如酯基、碳酸酯基、酮基等 [9～ 12 ] .因此 ,用活性聚合的方法对自由基开环聚合的分子量和分子量分布进行控制 ,可以制备出具有各种不同结构和性能的新聚合物 . Wei等 [13] 报道了利用稳定自由基法实现…     

锡苯和铅苯二聚反应的理论研究

采用密度泛函理论B3LYP方法,研究了锡苯和铅苯的[2+2],[4+2]及[4+4]二聚反应的微观机理和势能剖面,考察了Sn(Pb)原子上的2,4,6-三甲基苯基(Mes)取代基对反应势能剖面的影响.研究结果表明,所有反应均为协同过程,且大多数情况下,2个C—Sn(Pb)键同步形成.[2+2]和[4+2]反应在热力学和动力学上均比相应的[4+4]反应容易进行,而[4+2]反应在动力学上比相应的[2+2]反应有利.Sn(Pb)原子上的Mes取代基在热力学和动力学上均不利于反应的进行.铅苯的动力学稳定性与锡苯相当,但其热力学稳定性高于锡苯.     

CH_2(~3B_1)自由基与N_2O反应的研究

CH2是燃烧和大气光化学中重要的自由基之一[1]．在燃烧过程中,CH2自由基由碳氢化合物分子热解或由O原子和C2H2等反应生成．这种高活性的中间体,又可进一步与燃烧过程中其它重要物质如NOx（NO、NO2、N2O）发生反应．在低温燃烧过程中,N2O是NOx存在的主要形式,所以,研究CH2自由基与N2O的反应,对于了解燃烧机制有重要意义．就我们所知,关于CHZ和N20的反应,国内外还未见文献报导．本文从态-态反应的层次上,开展基电子态CH2（X3B1）自由基与N2O反应的实验研究．我们利用351um紫外激光光解CH2CO产生CH2自由基,这种方法…     

“时钟反应”及其非恒容修正

化工生产中有不少是动态非恒容体系，例如不断地向反应器中添加溶液。曾有人利用“时钟反应”对此种体系进行研究。如文献[1]是在砷酸缓冲溶液中于较大容积内反应，文献[2]则以稀硫酸为介质进行实验。其主要目的都是通过测定宏观动力学参数来揭示反应机理和第一     

p-硝基氯苯与α氰基乙酸乙酯-α-碳负离子的电子转移反应动力学研究: 非链式的自由基机理

在ρ-硝基氯苯(1)与α-氰基乙酸乙酯-α-碳负离子(2)的反应过程中,测得了反应中间体ρ-硝基氯苯负离子自由基(3)的ESR谱.用ESR场/频联锁技术测定了(3)的ESR吸收强度-时间曲线,当[1]<<[2]时,其结果与连续一级反应动力学相吻合.测得了从2向1的电子转移和3的分解反应速率常数和活化参数.反应产物为α-氰基α-(ρ-硝基苯基)乙酸乙酯和微量的硝基苯.为该反应提出了非链式的电子转移-负离子自由基分解-自由基偶合机理.     

p-硝基氯苯与α氰基乙酸乙酯-α-碳负离子的电子转移反应动力学研究: 非链式的自由基机理

在p-硝基氯苯(1)与α-氰基乙酰乙酯-α-碳负离子(2)的反应过程中, 测得了反应中间体p-硝基氯苯负离子自由基(3)的ESR谱。用ESR场/频联锁技术测定了(3)的ESR吸收强度-时间曲线, 当[1]《[2]时, 其结果与连续一级反应动力学相吻合。测得了从2向1的电子转移和3的分解反应速率常数和活化参数, 反应产物为α-氰基-α-(p-硝基苯基)乙酸乙酯和微量的硝基苯。为该反应提出了非链式的电子转移-负离子自由基分解-自由基偶合机理。     

NO reburning study based on species quantification obtained by coupling LIF and cavity ring-down spectroscopy

NO reburning is studied in a low pressure (15 hPa) premixed flame of CH4-O2 seeded with 1.8% of NO. Measurements were carried out by using cavity ring-down spectroscopy (CRDS) and laser induced fluorescence (LIF) techniques. The temperature profile was obtained by OH-LIF thermometry in the A-X (0-0) band. The OH profile was determined by LIF and calibrated by single pass absorption. The NO concentration profile was obtained by LIF in the A-X (0-0) band and corrected for Boltzmann fraction and quantum yield variations. The absolute concentration profile was determined in the burned gases by CRDS allowing a direct experimental determination of the NO reburning amount. Finally CH and CN mole fraction profiles were obtained by CRDS by exciting rotational transitions in the B-X (0-0) bands of CH and CN around 387 nm. We found a peak mole fraction of 29 ppm for CH and 3.3 ppm for CN. This last result is in contrast with a previous study of W. Juchmann, H. Latzel, D. L. Shin, G. Peiter, T. Dreier, H. R. Volpp, J. Wolfrum, R. P. Lindstedt and K. M. Leung, XXVIIth Symposium (International) on Combustion, The Combustion Institute, Pittsburgh, 1998, p. 469, performed in a similar flame, which reported much lower levels of CN. In that study the absolute concentration of CN was indirectly obtained by LIF calibrated by Rayleigh scattering. In a second part, experimental species profiles are compared with predictions of the GRI 3.0 mechanism. Comparison between experimental and predicted profiles shows a good agreement particularly for CN and NO species. A qualitative analysis of NO reburning is then performed.     

Measurements of density and sticking probability of CN(X(2)Sigma(+)) radicals by laser-induced fluorescence spectroscopy

CN(X(2)Sigma(+)) radicals were produced by the decomposition of BrCN with the microwave discharge flow of Ar under the conditions of Ar pressure in the range of 0.40-0.70 Torr. The laser-induced fluorescence (LIF) spectra of the CN(A(2)Pi(i)-X(2)Sigma(+)), 4-0, 5-1, and 7-2 bands were observed, and their intensities were calibrated against Rayleigh-scattering intensity by Ar atoms, from which the CN(X(2)Sigma(+)) radical density (n(CN(X))) was determined as (0.67+/-0.25) x 10(18) to (4.42+/-0.83) x 10(18) m(-3). Hydrogenated amorphous carbon nitride (a-CN(x):H) films were formed by depositing the CN(X(2)Sigma(+)) radicals on Si substrates in the same reaction system as LIF. The sticking probability (s) of the CN(X(2)Sigma(+)) radicals onto the a-CN(x):H films was determined by using n(CN(X)), the flow speed, and the weight (w) of a-CN(x):H. The s value was determined as (6.4+/-6.4) x 10(-2) to (2.5+/-1.2) x 10(-2), where the errors are predominantly determined by those in n(CN(X)) and w. The procedure described in the present study will provide a methodology to determine the sticking probability of the precursor radicals of the film formation based on the gas-phase LIF spectroscopy.     

Ultraviolet spectroscopy of pyrene in a supersonic jet and in liquid helium droplets

In a series of experiments devoted to the study of polycyclic aromatic hydrocarbons for astrophysical applications, the S(2)<--S(0) transition of jet-cooled pyrene (C(16)H(10)) at 321 nm has been studied by an absorption technique for the first time. The spectra observed by cavity ring-down spectroscopy closely resemble the excitation spectra obtained earlier by laser-induced fluorescence (LIF) and show the same band clusters arising from the vibronic interaction of S(2) with S(1). We have also investigated pyrene when it was incorporated into 380 mK cold helium droplets. These spectra which were recorded employing LIF and molecular beam depletion spectroscopy are broadened and redshifted by 0.94 nm but retain the essential features of the gas phase spectra.     

Detection of CN radicals in DC nitrogen plasma used for deposition of CNx layers

Emission spectra from a DC plasma discharge of nitrogen with a graphite cathode used for deposition of CNx layers were investigated in the visible range 350-900 nm. The spectra recorded at low and high resolution from both the negative glow and the positive column of the discharge were studied separately. All spectra are dominated by neutral and ionised N2 emission. In the positive column the violet band of the cyanogen (CN) radical was identified and analysed for vibrational structure. From a computer simulation of the rotationally resolved violet band, vibrational temperatures were derived and found to be in the intensity distribution for the nu = 0, 1 and 2 levels from thermal equilibrium. In the negative glow the strong N2+ features completely mask the spectral region of the violet band of CN. Conclusions were drawn concerning the CN formation by chemical sputtering, and the role of CN radicals in the formation of polymeric CNx layers of 1:1 = C:N stoichiometry.     

Direct on-strip analysis of size- and time-resolved aerosol impactor samples using laser induced fluorescence spectra excited at 263 and 351 nm

We report a novel atmospheric aerosol characterization technique, in which dual wavelength UV laser induced fluorescence (LIF) spectrometry marries an eight-stage rotating drum impactor (RDI), namely UV-LIF-RDI, to achieve size- and time-resolved analysis of aerosol particles on-strip. The UV-LIF-RDI technique measured LIF spectra via direct laser beam illumination onto the particles that were impacted on a RDI strip with a spatial resolution of 1.2 mm, equivalent to an averaged time resolution in the aerosol sampling of 3.6 h. Excited by a 263 nm or 351 nm laser, more than 2000 LIF spectra within a 3-week aerosol collection time period were obtained from the eight individual RDI strips that collected particles in eight different sizes ranging from 0.09 to 10 μm in Djibouti. Based on the known fluorescence database from atmospheric aerosols in the US, the LIF spectra obtained from the Djibouti aerosol samples were found to be dominated by fluorescence clusters 2, 5, and 8 (peaked at 330, 370, and 475 nm) when excited at 263 nm and by fluorescence clusters 1, 2, 5, and 6 (peaked at 390 and 460 nm) when excited at 351 nm. Size- and time-dependent variations of the fluorescence spectra revealed some size and time evolution behavior of organic and biological aerosols from the atmosphere in Djibouti. Moreover, this analytical technique could locate the possible sources and chemical compositions contributing to these fluorescence clusters. Advantages, limitations, and future developments of this new aerosol analysis technique are also discussed.     

配合物Cr(CN) ,Co(CN) , COF 光谱的Xα理论研究

应用考虑重叠修正项多重散身Xα自洽场方法,详细研究其重叠修正项对过渡金属配合物分子的价电子轨道的影响,进一步利用不可约张量方法,发展一种求解多体Schrodinger方程的方法. 将该方法应用于计算Cr(CN) ,Co(CN) , COF 的d-d跃迁能,其结果优于其它理论方法的计算结果.计算结果还表明Xα方法中重叠修正项对多体问题有一定的影响.     

Reaction dynamics of V(a4FJ)+NO-->VO(X 4Sigma-)+N studied by a crossed-beam laser-induced fluorescence technique

The dynamics of the reaction, V(a 4FJ)+NO-->VO(X 4Sigma-)+N was studied by using a crossed-beam technique at 16.4 kJ/mol of collision energy. The V atomic beam was generated by laser vaporization and crossed with the O2 beam at a right angle. The laser-induced fluorescence (LIF) for the transition of VO(B 4Pi-X 4Sigma) was used to determine the rotational state distribution of the reaction product in the vibrational ground state. Almost pure V(a 4FJ) beam was obtained by using the mixture of NH3 with N2 as a carrier gas. Comparing the LIF spectra of VO measured for two carrier gases, i.e., NH3N2 and pure N2, it was concluded that the vibrational ground state of VO(X 4Sigma-) is formed almost entirely from the reaction of V(a 4FJ) and the contribution of the metastable V(a 6DJ) is negligible. The observed rotational distribution was similar to a statistical prior prediction, and suggested that the title reaction proceeds via a long-lived intermediate, which is consistent with an electron transfer mechanism.     

Ultrafast tabletop laser-pump-x-ray probe measurement of solvated Fe(CN)6 4-

We report on the first ultrafast laser-pump-picosecond x-ray probe measurements of solvated transition metal complexes carried out with a tabletop ultrafast laser-driven plasma x-ray source. The x-ray absorption fine structure (XAFS) spectra of Fe(CN)(6) (4-) solvated in water have been measured before and tens of picoseconds after photoexcitation with ultrashort UV laser pulses. The XAFS spectra after photoexcitation exhibits a K-edge shift indicating the increase of the iron-ligand distances. Reference spectra of Fe(CN)(6) (4-) and Fe(CN)(6) (3-) measured at a synchrotron source yield structural data that show static solvation-induced bond length changes of the metal complexes.     

Differential scattering cross-sections for CN A2Pi+Ar

We present the first results from a novel experimental approach to the measurement of state-to-state differential scattering cross-sections for inelastic scattering of electronically excited CN A(2)Pi with Ar. Photodissociation of ICN with linearly polarized 266 nm radiation generates CN X(2)Sigma(+) (upsilon(")=0,J(")) with a near mono-energetic speed distribution and large anisotropy. Saturated optical pumping of the nascent CN X(2)Sigma(+) transfers this speed distribution without distortion to selected rotational quantum states of the A(2)Pi (upsilon(')=4) level. The products of rotational energy transfer within the A(2)Pi (upsilon(')=4) level into the J(')=0.5, F(2), f, state are probed using frequency modulated stimulated emission spectroscopy on the A-X (4,2) band with a single frequency external cavity tunable diode laser. Doppler profiles of transitions from individual rotational, spin-orbit and lambda doublet specific levels are acquired for different geometrical arrangements of photolysis polarization and probe propagation directions. The resulting Doppler profiles, which for this J(')=0.5 state cannot display a rotational angular momentum alignment, are combined to yield composite Doppler profiles depending on speed and translational anisotropy, which are analyzed to determine fully state-to-state resolved differential scattering cross-sections.     

High-spin alkali trimers on helium nanodroplets: spectral separation and analysis

Electronic excitation spectra of homo- (K(3),Rb(3)) and heteronuclear (K(2)Rb,KRb(2)) alkali trimers in the high-spin quartet state have been investigated in a broad spectral range (10,600-17,400 cm(-1)). Ten new bands showing laser induced fluorescence (LIF) were measured. Due to the pickup statistics, overlapping spectra of all possible oligomers are present at once, complicating the unraveling and assignment of individual spectra. To circumvent the problem, two variations of beam depletion spectroscopy were employed in addition to the conventional analysis of the relation between signal and pickup pressure: A two-laser V-type double resonance scheme combining beam depletion with LIF, and a mass selective beam depletion scheme. In principle, these allow accurate separation of an arbitrary number of overlapping spectra. The benefits and drawbacks of each method are discussed. Assignment to electronic states is achieved by comparison with ab initio complete active space self-consistent field calculations of the excited electronic level structure of the molecules.