烷烃类分子对NC0（A^2∑^＋）自由基的猝灭

采用激光光解—激光诱导荧光(LP—LIF)的方法，用266nm激光光解CHBr3分子产生CH自由基，再与N2O继续反应作为NCO自由基的产生源，用438．6nm激光将电子基态X^2∏i(00^10)的NCO激励到激发态A^2∑^+(00^00)上，通过检测激发态NCO时间分辨荧光信号，测得室温(298K)下NCO(A^2∑^+)被烷烃类分子猝灭的实验结果，获得了A^2∑^+(00^00)态猝灭速率常数．实验发现，随着烷烃分子中C—H键数增加，其猝灭截面也近线性增加，但随着分子体积增大，这种增加趋缓．     

烷烃类分子对NCO(A2∑+)自由基的猝灭

采用激光光解 激光诱导荧光 (LP LIF)的方法 ,用 2 6 6nm激光光解CHBr3 分子产生CH自由基 ,再与N2 O继续反应作为NCO自由基的产生源 ,用 4 38.6nm激光将电子基态X 2 Πi(0 0 10 )的NCO激励到激发态A2 Σ+ (0 0 0 0 )上 ,通过检测激发态NCO时间分辨荧光信号 ,测得室温 (2 98K)下NCO(A2Σ+ )被烷烃类分子猝灭的实验结果 ,获得了A 2Σ+ (0 0 0 0 )态猝灭速率常数 .实验发现 ,随着烷烃分子中C -H键数增加 ,其猝灭截面也近线性增加 ,但随着分子体积增大 ,这种增加趋缓 .     

NCO异构体结构与分析势能函数

在B3LYP/6-31+G(d)水平上,对NCO分子的各种可能结构进行几何优化,得到了NCO及其异构体分子CNO和CON基态结构都是C∞v,电子态为X 2Π,NCO分子的平衡核间距RNC=0.1230nm, RCO=0.1186nm,离解能De=13.40eV,并计算出谐振频率ω1=1293.44cm-1, ω2(A΄)=484.73cm-1,ω2(A˝)=559.72cm-1,ω3=1988.41cm-1,Renner-Teller参数ε=-0.1429,计算值与实验值吻合较好．在此基础上,应用多体项展式理论,单体项中首次引入开关函数,三体项以NCO,CNO基态结构与性质为依据,拟合给出了NCO分子的基态分析势能函数,其等值势能图准确再现了NCO,CNO分子基态结构与特征,并与优化结果完全一致．     

NCO异构体结构与分析势能函数

在B3LYP/6-31+G（d）水平上,对NCO分子的各种可能结构进行几何优化,得到了NCO及其异构体分子CNO和CON基态结构都是C_∞v,电子态为X²Ⅱ,NCO分子的平衡核间距R_NC=0.1230 nm,R_CO=0.1186 nm,离解能D_e=13.40 eV,并计算出谐振频率ω₁=1293.44 cm^-1,ω₂（A′）=484.73 cm^-1,ω₂（A″）=559.72 cm^-1,ω₃=1988.41 cm^-1,Renner-Teller参数ε=-0.1429,计算值与实验值吻合较好.在此基础上,应用多体项展式理论,单体项中首次引入开关函数,三体项以NCO,CNO基态结构与性质为依据,拟合给出了NCO分子的基态分析势能函数,其等值势能图准确再现了NCO,CNO分子基态结构与特征,并与优化结果完全一致.     

均相条件下NO与CO、NCO的反应机理研究

基于量子化学密度泛函理论研究了NO与CO、NCO在均相条件下的反应机理并进行了动力学和平衡常数的分析. CO与NO的均相反应存在两条反应路径：两者首先反应形成中间体CNO₂,CNO₂不易稳定存在,其继续与CO、NO反应分别生成NCO、N₂O. NCO的生成速率大于N₂O,但两条反应路径的反应速率常数都很小.与已发现的反应路径相比,反应中间体CNO₂可以降低均相条件下CO与NO的反应能垒,分析发现CNO₂中的N原子是易发生反应的活性位点. NCO与NO的反应同样存在两条路径,优势反应路径随温度升高而改变,但非优势路径对反应的贡献不能忽略,分析平衡常数可知N₂的存在对反应影响可以忽略,因此燃烧环境中NCO与NO的反应既生成N₂O和CO,也生成N₂和CO₂.     

CF2自由基与HNCO反应机理的量子化学研究

采用密度泛函理论B3LYP 方法研究了CF2 自由基与HNCO 的反应机理, 并在B3LYP/6-311＋＋G**水平上对反应物、中间体、过渡态进行了全几何参数优化, 通过频率分析和内禀反应坐标(IRC)确定了中间体和过渡态.为了得到更精确的能量值, 又用CCSD(T)/6-311＋＋G**方法计算了在B3LYP/6-311＋＋G**水平优化后的各个驻点的相对能量. 根据统计热力学及用Winger校正的Eyring过渡态理论,利用自编程序,计算不同温度下低势垒反应的平衡常数和速率常数.计算结果表明单重态的CF2 自由基与HNCO 的反应有四条反应通道, 三重态的CF2 自由基与HNCO 的反应有两条反应通道.其中单重态反应通道CF2＋HNCO→1IM1→1TS1→1IM2→1TS2→1IM3→CF2NH＋CO(P1)为主反应通道.三重态反应通道CF2＋HNCO→36IM1→36TS1→36IM2→HCF2+NCO(3P5)为主反应通道.     

CF2自由基与HNCO反应机理的量子化学研究

采用密度泛函理论B3LYP 方法研究了CF2 自由基与HNCO 的反应机理, 并在B3LYP/6-311＋＋G**水平上对反应物、中间体、过渡态进行了全几何参数优化, 通过频率分析和内禀反应坐标(IRC)确定了中间体和过渡态.为了得到更精确的能量值, 又用CCSD(T)/6-311＋＋G**方法计算了在B3LYP/6-311＋＋G**水平优化后的各个驻点的相对能量. 根据统计热力学及用Winger校正的Eyring过渡态理论,利用自编程序,计算不同温度下低势垒反应的平衡常数和速率常数.计算结果表明单重态的CF2 自由基与HNCO 的反应有四条反应通道, 三重态的CF2 自由基与HNCO 的反应有两条反应通道.其中单重态反应通道CF2＋HNCO→1IM1→1TS1→1IM2→1TS2→1IM3→CF2NH＋CO(P1)为主反应通道.三重态反应通道CF2＋HNCO→36IM1→36TS1→36IM2→HCF2+NCO(3P5)为主反应通道.     

用TR-FTIR研究CH＋NO2的反应

CH自由基是烃类燃烧过程中反应活性很高的重要的中间产物[1,2].CH自由基与氮氧化物的反应被认为是通过二次燃烧过程减少氮氧化物的主要反应之一,也是对火焰中氮化物的化学行为建立模型的关键步骤[3].但是,对于CH与NO2反应的研究还不是很深入,到目前为止,只有两篇论文报道了该反应在298K时的总包反应速率常数[4,5].Taeg和Hershberger用红外二极管激光吸收法研究了该反应[6].他们在实验中只观测到了产物CO和NO,但一些较低能量的产物,如NH+CO2、OH+NCO等却没有被观察到.为了更深一步了解CH与NO2的反应产物及反应通道,我们用时间分…     

预混气体自由基点火的机理研究

本文通过渐近理论分析研究了预混气体的自由基点火。采用包含自由基动力学的两步化学反应,基于火焰球模型,推导出了描述火焰球半径随热点火能和自由基点火能以及燃料与自由基的Lewis数的关系式。并在此基础上分别分析了不存在热点火和存在热点火时自由基点火的临界条件,研究了燃料与自由基的Lewis数对最小自由基点火能的影响。研究结果表明:仅存在自由基点火时,最小自由基点火能随着自由基Lewis数的增加而减小,但燃料Lewis数对最小自由基点火能无影响。     

FTIR研究半预聚物法聚氨酯脲密封材料固化过程的表观动力学及氢键化作用

采用原位FTIR技术跟踪了半预聚物法聚醚型聚氯酯脲的固化过程,研究了其固化过程的宏观动力学.原位FTIR的光谱数据表明,随着反应时间的增加.脲键羰基的吸收逐渐增强,脲羰基的波数位置呈阶跃式向低波数方向移动.脲键羰基的氢键化作用逐渐增强.不含催化剂时,硬段优先形成,不利于NCO与OH的反应.氨酯羰基的峰高增加缓慢.脲键的生成对NCO/OH反应生成氨酯键无催化作用.     

DFT study of isocyanate chemisorption on Cu(100): Correlation between substrate–adsorbate charge transfer and intermolecular interactions

The adsorption of isocyanate (? NCO) species on Cu(100) was studied using the density functional theory (DFT) and the periodic slab model. The calculations indicate that at low and intermediate coverages NCO adsorbs preferentially on bridge and hollow sites. Work function and dipole moment changes show a significant negative charge transfer from Cu to NCO. The resulting charged NCO species interact repulsively among themselves being these dipole–dipole interactions particularly intensive when they are adsorbed in adjacent sites. Consequently, isocyanates tend to be separated from each other generating the vacant sites required for the dissociation to N and CO. This condition for NCO dissociation has been suggested in the past from experimental observations. A comparison was also performed with the NCO adsorption on Pd(100). In particular, the calculated minimal energy barrier for NCO dissociation was found to be higher on Cu(100) than on Pd(100) in accord with the well known higher NCO stability on Cu(100).     

Orientation and bonding of adsorbed CH3NCO on Pt{110} and Cu{110} from vibrational and photoelectron spectroscopies

The bonding and orientation of CH{in3}NCO on Pt{110} and Cu{110} are studied by HREELS, ARUPS, AES, and LEED. CH{in3}NCO is found to adsorb nondissociatively on both Cu{110} and Pt{110} at T = 160 K, bonding primarily through the 2π a′ orbital with the NCO group lying down on the surface and the methyl group largely unperturbed. We propose that the absence of a strong HREELS band at about 2290 cm^?1, which is the liquid phase frequency for the NCO asymmetric stretching mode, combined with the presence of strong bands between 1000 and 1450 cm^?1 provides a “finger-print” for NCO bonded to the surface in a lying-down configuration.     

Chemisorption of isocyanate (NCO) on the Pd(1 0 0) surface at different coverages

The chemisorption of isocyanate (NCO) species on Pd(1 0 0) was studied within the density functional formalism (DFT) using a periodic slab model. The NCO was adsorbed on top, bridge and hollow sites of the metal surface at different coverages. At low coverages, the adsorption energies are in the range of ?2.5/?3.0 eV, indicating an important adsorbate–substrate interaction for the three sites studied. The lateral repulsive interaction between neighboring NCO species is almost negligible or weak at lower and intermediate coverages, and very strong at complete monolayer. At low coverages, both bridge and hollow sites are energetically preferred; yet the bridge site becomes the only favoured site at intermediate and complete coverages. Work function and dipole moment calculations can be interpreted by an important charge transfer from the metal surface to NCO. Interestingly, while on hollow site the charge taken by NCO is essentially the same over all the range of coverage, an increasing depolarization is observed on bridge and top sites as the coverage increases. Symmetric and asymmetric NCO stretching modes were also calculated and compared with recent infrared spectroscopy measurements.     

Exploration of structural,optical, and photoluminescent properties of (1-x)NiCo2O4/xPbS nanocomposites for optoelectronic applications

The (1-x)NiCo₂O₄/xPbS (0≤ x≤ 0.2) nanocomposite samples are synthesized using the hydrothermal and thermolysis procedures. The different phases developed in the obtained nanocomposite samples are accurately determined using the x-ray diffraction technique equipped with a line-detector. The percentage of the formed phases (NiCo₂O₄ (NCO), PbS, PbSO₄), structural and microstructure parameters are determined using Rietveld quantitative phase analysis. The transmission electron microscope (TEM) images and Rietveld analysis reveal almost isotropic particle size in the nano range with a very narrow size distribution. The obtained phase percentage of PbS and PbSO₄ are smaller than nominated values (x) suggesting dissolving of some Pb and S ions into NCO which is then confirmed by the analysis of Fourier-transform infrared (FTIR) spectra of nanocomposite samples. The absorption spectra are modified upon doping NCO with PbS. The optical band gaps of the nanocomposites increase as the amount of PbS augments. The effect of alloying on extinction coefficient, refractive index, dielectric constant, optical conductivity, the intensity, and emitted color from the photoluminescence of the nanocomposite samples are also studied. The refractive index value of NCO and NCO-PbS nanocomposite samples exhibit normal dispersions. The photoluminescent measurements reveal that the NCO-PbS nanocomposites can emit a violet color. The improvement in the values of the nonlinear optical (NLO) parameters of pristine NCO at high frequencies or the nanocomposite samples at low frequencies, are made them used in NLO photonic devices.     

Adsorption and decomposition of HNCO on Cu(111) surface studied by auger electron,electron energy loss and thermal desorption spectroscopy

No detectable adsorbed species were observed after exposure of HNCO to a clean Cu(111) surface at 300 K. The presence of adsorbed oxygen, however, exerted a dramatic influence on the adsorptive properties of this surface and caused the dissociative adsorption of HNCO with concomitant release of water. The adsorption of HNCO at 300 K produced two new strong losses at 10.4 and 13.5 eV in electron energy loss spectra, which were not observed during the adsorption of either CO or atomic N. These loses can be attributed to surface NCO on Cu(111). The surface isocyanate was stable up to 400 K. The decomposition in the adsorbed phase began with the evolution of CO₂. The desorption of nitrogen started at 700 K. Above 800 K, the formation of C₂N₂ was observed. The characteristics of the CO₂ formation and the ratios of the products sensitively depended on the amount of preadsorbed oxygen. No HNCO was desorbed as such, and neither NCO nor (NCO)₂ were detected during the desorption. From the comparison of adsorption and desorption behaviours of HNCO, N, CO and CO₂ on copper surfaces it was concluded that NCO exists as such on a Cu(111) surface at 300 K. The interaction of HNCO with oxygen covered Cu(111) surface and the reactions of surface NCO with adsorbed oxygen are discussed in detail.     

Absorption Spectrum Study on Colloidal Centers in KCl:NCO:K

The absorption spectrum study on metallic colloidal centers in KCl:NCO:K crystals have been performed as a function of annealing temperature in the temperature range of 500–750K. Conversion process between F-centers and colloidal centers was observed and it is found that the NCO ions play an important role in the formation and stability of aggregative centers in alkali halides.     

Thermal stability of adsorbed CH3NCO on Cu{110} AND Pt{110} from vibrational and photoelectron spectroscopies

The thermal stability of CH₃NCO adsorbed on Cu{110} and Pt{110} is investigated using HREELS, TPD, and ARUPS. CH₃NCO desorbs largely without fragmentation from Cu{110}, but on Pt{110} only about 20% of the adsorbed CH₃NCO desorbs intact, with 80% decomposing on the surface at T > 200 K into CO(a), H(a), CH_x(a), N(a) and NH_y(a) fragments. The kinetics of the surface decomposition were characterised for 220 < T < 300 K by HREELS and the activation energy for CH₃NCO decomposition was found to vary strongly as a function of coverage.     

Effects of preadsorbed oxygen on the formation and decomposition of NCO on Rh(111) surfaces

The interaction of HNCO with oxygen dosed Rh(111) surface has been investigated by Auger electron, electron energy loss and thermal desorption spectroscopy. The presence of adsorbed oxygen exerted no apparent influence on the weakly adsorbed HNCO (T_p = 130 K). It promoted, however, the dissociative adsorption of HNCO by forming a strong O—H bond which prevented the associative desorption of HNCO. As a result no H₂ and NH₃ formation occurred, in contrast with the clean surface, and the surface concentration of irreversibly bonded NCO was also increased. New products of the surface reaction were H₂O and CO₂, in addition to CO and N₂ observed on a clean surface. From the behavior of the losses characteristic for the adsorbed NCO it appeared that the preadsorbed oxygen exerted a significant stabilizing effect on the NCO bonded to the Rh.     

Spin dynamics in LiCu<Subscript>2</Subscript>O<Subscript>2</Subscript> and NaCu<Subscript>2</Subscript>O<Subscript>2</Subscript> low-dimensional helical magnets

Comprehensive NMR investigation of low-frequency spin dynamics of LiCu₂O₂ (LCO) and NaCu₂O₂ (NCO) low-dimensional helical magnets in the paramagnetic state has been carried out for the first time. Temperature dependences of the spin–lattice relaxation rate and anisotropy on various LCO/NCO nuclei have been determined at various orientations of single crystals in an external magnetic field. The spatial asymmetry of spin fluctuations in LCO multiferroic has been discovered. The quantitative analysis of the anisotropy of spin–lattice relaxation in LCO/NCO has allowed estimating the contributions of individual neighboring Cu²⁺ ions to the transferred hyperfine field on Li⁺(Na⁺) ions.