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通过具体实例说明对于气相反应,使用基于压力的速率方程解题比使用基于浓度的速率方程更直接﹑更简便。总结了具有简单级数的反应的基于压力的速率方程及其特征。 相似文献
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以直线交叉法为依据,根据最小二乘原理,采用Matlab GUI工具设计了一款用于计算二元共聚合反应竞聚率的图形用户程序。与传统的求解竞聚率方法相比,该图形用户程序具有设计原理简单、计算快捷的特点;同时程序提供界面简洁、交互友好的数据输入平台,实用性强。实际应用表明:采用该款图形用户程序所测得的数据与微机动态搜索法、Tidwell-Mortimer法相近,而比采用斜率截距法计算竞聚率的最小差方和更小,并且也避免了采用斜率截距法由于所用方程的非对称性造成的计算结果的不一致性。 相似文献
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众所周知,物理力学性能是照相明胶的一种很重要的属性。在各种彩色及黑白胶片都面向高温快速加工发展的今天,这种属性就显得更为重要。提高胶片的物理力学性能,一方面要从提高明胶本身的胶冻强度着手,例如减少明胶中溶胶组份(分子量小、冷水中溶解度高),提高明胶中的α和β组份的相对含量,减少分子量过大的组份等等。 相似文献
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体毛的化学和头发的保护 总被引:1,自引:0,他引:1
本文介绍了体毛结构和功能的一般化学基础,讨论了毛发的化学特征如氨基酸及微量元素的组成和应用依据,研究了护发的化学方法。作为皮肤附属器官的体毛,特别是头发,除一般的美容化妆外,近10多年来还由于人体微量元素研究的进展而引起人们的重视。曾多次召开过国际人发研究学术讨论会[1],国际原子能研究机构(IAEA)还在全球范围内收集了人发数据,并发布了人发标样(IAEA-HH-1),我国也研制了类似的标准物。在各种病因诊断、法医学研究中,头发分析是重要项目。而在日常消费新潮中,青年人也常把相当多的精力和金钱投放在发型的美化上。因此体毛的化学和头发的保护问题,日益成为化学与生活联系的重要渠道,其社会意义已不容忽视。本文尝试就毛发的结构、功能、组成及可能的病交的化学基础和有关化妆的化学信息作一简介。 相似文献
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在地球的低层地幔下 ,可能存在着比现在的海洋还要多 4倍的水 ,这是日本工业大学的M .Murakami和他的同事们最近估测出来的。日本地球科学家们利用了一种多功能钻探仪 ,通过对 3种据信包含低层地幔中在高温高压下生成的主要矿物组成的分析后 ,得到了这个结论。这 3种矿物是 :Mg perovskite ,Ca perovskite和Magnesiow櫣stite。再利用SIMS对矿物中溶解的氢的含量进行测量 ,矿物学家认为氢是水的标记。发现这3种矿物的含水量都相当可观 ,大约在 0 .2 %至 0 .4 %(重量比率 )之间。用红外… 相似文献
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A comparison of eight density functional models for predicting the molecular structures, vibrational frequencies, infrared intensities, and Raman scattering activities of platinum(II) antitumor drugs, cisplatin and carboplatin, is reported. Methods examined include the pure density functional protocols (G96LYP, G96PW91, modified mPWPW and original PW91PW91), one‐parameter hybrid approaches (mPW1PW and mPW1LYP), and three‐parameter hybrid models (B3LYP and B3PW91), as well as the HF and MP2 levels of theory. Different effective core potentials (ECPs) and several basis sets are considered. The theoretical results are discussed and compared with the experimental data. It is remarkable that the mPW1PW protocol introduced by Adamo and Barone [J Chem Phys 1998, 108, 664], is clearly superior to all the remaining density functional methods (including B3LYP). The geometry and vibrational frequencies of cisplatin and carboplatin calculated with the mPW1PW method, and the ECP of Hay and Wadt (LanL2DZ basis set) are in better agreement with experiment than those obtained with the MP2 method. The use of more elaborated ECP and the enlargements of basis sets do not significantly improve the results. A clear‐cut assignments of the platinum‐ligand vibrations in cisplatin and carboplatin are presented. It is concluded that mPW1PW is the new reliable method, which can be used in predicting molecular structures and vibrational spectra of large coordination compounds containing platinum(II). © 2001 John Wiley & Sons, Inc. J Comput Chem 22: 901–912, 2001 相似文献
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用密度泛函理论(DFT)研究了Cu(001)表面CO吸附单层的表面性质. 总能计算结果表明, 顶位结构总能最低, 相应位置的CO分子吸附能最大. 谷位吸附结构的衬底原子层间距相对于清洁表面的膨胀量约为10%, 从而导致了谷位吸附的不稳定性. 在顶位、桥位和谷位三个吸附结构中, C和Cu原子之间的距离dC-Cu分别为0.1868、0.1975和0.2231 nm, 对应的CO分子键长为0.1154、0.1165 和0.1175 nm. 计算了CO分子的态密度(DOS). 结果表明, 衬底与分子的作用主要是分子和金属轨道的杂化. 在吸附过程中, 电荷主要从碳原子的s轨道向p轨道转移. 在顶位、桥位和谷位吸附结构中, 每个碳原子内电荷的转移量分别为0.45e、0.54e 和0.55e. 衬底向吸附分子的电荷转移量不大, CO 吸附分子层为一绝缘层. 相似文献
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采用广义梯度近似GGA,修正Perdew—Burke—Ernzerhof交换-关联泛函,以及周期性切片模型对O2、CO2和H2O在UN(001)表面的化学吸附行为进行非白旋极化水平的密度泛函理论计算.在四个对称性化学位置条件下,对化学吸附能与分子和UN(001)表面之间距离的关系曲线进行优化.结果表明O2、CO2和H2O分子的最稳定吸附位置分别为桥式平行、空心平行和桥式H向上,化学吸附能分别为14.127、4.421和5.736kJ/mol.从吸附物UN(001)表面角度考虑,O2与UN(001)表面之间的相互作用最高,然后为CO2和H2O,表明这些相互作用与吸附物的晶体结构相关.O2化学吸附导致UN(001)表面的N原子向基体内部迁移,而CO2和H2O化学吸附对UN(001)表面分别具有中等和忽略不计的效应.计算获得的态密度显示了化学吸附分子S、P轨道和U6d、U5f轨道之间的电子电荷转移行为. 相似文献
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The adsorption and reaction of O + CN → OCN on Cu(100) are studied by using density functional theory and cluster model.Cu14 cluster model is used to simulate the surface.The calculated results show that the OCN species with the molecule perpendicular to the surface via N atom (N-down) is more favorable than other adsorption models, and the N-down at the bridge site is the most favorable.For N-down, calculated OCN symmetric and asymmetric stretching frequencies are all blue-shifted compared with the calculated values of free and in good agreement with the experiments.The charge transfer from the surface to the OCN species leads to that the bonding of OCN to the metal surface is largely ionic.The present studies also show that CN with the molecule perpendicular to the surface via C atom (NC-down) at the top site is the most stable.Except NC-down at the top site, the calculated CN stretching frequencies are all red-shifted.With O coadsorbed at the hollow site, the adsorption of NC-down at the next nearest bridge or top site is energetically more favorable than that at the adjacent hollow site.The reaction of O + CN → OCN on Cu(100) has no energy barrier via both Eley-Rideal and Langmuir-Hinshelwood processes. 相似文献
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The adsorption of H2O molecule and its dissociation products, O and OH, on CuCl(111) surface was studied with periodic slab model by PW91 approach of GGA within the framework of density functional theory. The results of geometry optimization indicate that the top site is stable energetically for H2O adsorbed over the CuCl(111) surface. The threefold hollow site is found to be the most stable adsorption site for OH and O, and the calculated adsorption energies are 309.5 and 416.5 kJ/mol, respectively. Adsorption of H2O on oxygen-precovered CuCl(111) surface to form surface hydroxyl groups is predicted to be exothermic by 180.1 kJ/mol. The stretching vibrational frequencies, Mulliken population analysis and density of states analysis are employed to interpret the possible mechanism for the computed results. 相似文献
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Geometrical,spectroscopic, and magnetic properties of an oxygen atom adsorbed on the Ni(100) surface
Annick Goursot Franca Mele Nino Russo Dennis R. Salahub Marirosa Toscano 《International journal of quantum chemistry》1993,48(5):277-286
Spin-polarized linear combinations of Gaussian-type orbital–model core potential–local spin density (LCGTO –MCP –LSD ) computations have been performed for oxygen chemisorption on a Ni(100) surface simulated by four different clusters. Results show that the oxygen atom chemisorbs preferentially on the fourfold hollow site with an equilibrium distance of 1.931 Å and a vertical vibrational frequency of 401 cm?1. The corresponding experimental values are 1.960 Å and 423 or 430 cm?1. A satisfactory agreement with experiment is also found for the adsorption energy (6.7 vs. 5.6 eV). The bridge position lies at only 0.4 eV above the fourfold hollow one. It is found that oxygen adsorption leaves the bare cluster total spin magnetic moment unchanged, but induces appreciable reductions of the local atomic moment on the surface nickel atoms. © 1993 John Wiley & Sons, Inc. 相似文献
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Small neutral, anionic, and cationic silver cluster hydrides AgnH and anionic HAgnH (n=1-7) have been studied using the PW91PW91 density functional method. It was found that the most stable structure of the AgnH complex (neutral or charged) does not always come from that of the lowest energy bare silver cluster plus an attached H atom. Among various possible adsorption sites, the bridge site is energetically preferred for the cationic and most cases of neutral Agn. For anionic Agn, the top site is preferred for smaller Agn within n相似文献
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Adsorption of cyclohexene and its dehydrogenation intermediates on nAu/Pt(100)(n=0,1,2) surfaces:A DFT study 下载免费PDF全文
Adsorption of cyclohexene and its dehydrogenation intermediates on the nAu/Pt(100) (n = 0, 1, 2 means clean Pt, one monolayer and two layers of Au covered Pt surfaces, respectively.) has been investigated by self-consistent (GGA-PW91) density functional theory combined with periodic slab model. It is found that on the clean platinum, there are two kinds of favorable adsorption sites, i.e., hollow sites and bridge sites, and the adsorption energy at the hollow site is larger than that at the bridge site. However, on the Au/Pt and 2Au/Pt surfaces, there are three kinds of adsorption sites, and the adsorption energies are alike at both the bridge site and the top site. The magnitude order of the adsorption energies is as follows: clean Pt > Au/Pt > 2Au/Pt. The configurations of cyclohexene molecule have been distorted a little during the geometry optimizations. The lengths of C–M (M = Pt or Au, on the top layer of the slab) bonds are closely related to the corresponding adsorption energies. 相似文献
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Ferral A Patrito EM Paredes-Olivera P 《The journal of physical chemistry. B》2006,110(34):17050-17062
The local structure of the sulfur atom of methanethiolate and ethanethiolate on the Cu(111) and Cu(100) surfaces was investigated from first principles employing the periodic supercell approach in the framework of density functional theory. On the 111 surface, we investigated the (square root 3 x square root 3)R30 degrees and (2 x 2) structures, whereas on the 100 surface, we investigated the p(2 x 2) and c(2 x 2) structures. The landscape of the potential energy surface on each metal surface presents distinctive features that explain the local adsorption structure of thiolates found experimentally. On the Cu(111) surface, the energy difference between the hollow and bridge sites is only 3 kcal/mol, and consequently, adsorption sites ranging from the hollow to the bridge site were observed for increasing surface coverages. On the Cu(100) surface, there is a large energy difference of 12 kcal/mol between the hollow and bridge sites, and therefore, only the 4-fold coordination was observed. The high stabilization of thiolates on the hollow site of Cu(100) may be the driving force for the pseudosquare reconstruction observed experimentally on Cu(111). Density of states analysis and density difference plots were employed to characterize the bonding on different surface sites. Upon interaction with the metal d bands, the pi* orbital of methanethiolate splits into several peaks. The two most prominent peaks are located on either edge of the metal d band. They correspond to bonding and antibonding S-Cu interactions. In the case of ethanethiolate, all the back-bonds are affected by the surface bonding, leading to alternating regions of depletion and accumulation of charge in the successive bonds. 相似文献