DEVELOPMENT OF THEORETICAL SURFACE SPECTRAL APPARATUS

理论表面光谱仪的研制

基本信息

批准号：
18550013
负责人：
ENDO Kazunaka
金额：
$ 2.63万
依托单位：
Kanazawa University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (C)
财政年份：
2006
资助国家：
日本
起止时间：
2006 至 2007
项目状态：
已结题

来源：
https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-18550013/
关键词：
ELECTRON SPECTRUM MASS SPECTROMETRY SOLID NMR MOLECULAR DYNAMICS MOLECULAR ORBITAL METHOD DENSITY FUNCTIONAL METHOD

项目摘要

We considered from two theoretical viewpoints of both (A) time-independent and (B) time-dependent Hamiltonian for the development of theoretical surface spectral apparatus, in order to simulate electron spectra of substances by surface scientific instruments, and to gain the mass spectra by MS and static or TOF SIMS, respectively.In (A), six kinds of spectral analyses were performed in the following way; (1) X-Ray Photoelectron and Carbon Kα Emission measurements and calculations of O-, CO-, N-, and S-containing Substances (The combined analysis of valence XPS and carbon Ka XES for PEO, PVA, PVME, PVMK, PET, P4VP, PAO, PPS polymers was performed to determine the individual contributions from pσ-, and pπ-bonding molecular orbitals of the polymers by DFT calculations. We calculated all CEBEs of the model molecules using the ΔE_ks approach. Our simulated Cls photoelectron and C Kα emission spectra are in good agreement with our measurements.), (2)Electronic structure of a Mn_12 molecular … More magnet: Theory and experiment, (3)Simulation of resonant X-ray emission spectra of ethylene and benzene molecules (We proposed a theoretical method for analysis of resonant X-ray emission spectra from ab initio MO calculation using single configuration approximation as an intermediate state.) (4)Theoretical analysis of Auger electron spectra of 2nd periodic element containing substances(Simulated AES and valence XES of four substances [graphite, GaN, SiO_2, LiF] by DFT calculations using model molecules are in considerably good accordance with the experimental ones. Experimental AES of the substances were classified in each range of 1s-2s2s, 1s-2s2p and 1s-2p2p transitions for C, N, 0 and F KVV' spectra, respectively.), (5)XPS Spectral Simulation of Chitosan in Thermal Decomposition Process (6)X-Ray Photoelectron Spectral Analysis for Carbon Allotropes (We performed DFT calculations using Amsterdam density functional (ADF) program to simulate X-ray photoelectron spectra for carbon allotropes (diamond, graphite, single-wall carbon nanotube(SWCN), and fullerene C_60). We firstly described the simulation method for valence electron spectra to distinguish the diamond phase of carbon from the graphite carbon, and secondly evaluated the WD values from the differences between the calculated core-electron binding energies(CEBE)s of the model molecules (using ΔE_ks approach(like ΔSCF method in MO))and experimental CEBEs of carbon allotropes. The WD values of carbon allotropes correspond to the order of experimental values (CNT < graphite < diamond < C_<60>) for work functions obtained from accurate cylindrical analyzer(CMA)detector by Goto's and co-workers.)In (B), three investigations were performed as follows; (1) Simulations of thermal decomposition for carbon allotrope molecules by a quantum molecular dynamics method (In order to simulate thermal decomposition of carbon allotrope molecules [single walled carbon nanotube(SWNT)models{arm-chair(C_<54>H_<12>), zigzag(C_<50>H_<10>) types), C_<60>, and graphic model C_<42>H_<16>], we used MD with semi-empirical AM1 MO method(a kind of QMD).) (2)Simulation of SIMS for monomer and dimer of lignin under the assumption of thermal decomposition using QMD method(The thermal decomposition of the monomer and dimer of lignin has been simulated by quantum molecular dynamics(DMD) method. We obtained the thermally decomposed fragments with positive, neural and negative changes from SCF MO calculation at each data of the last MD step, and simulated the fragment distribution of the monomer and dimer lignins from the last step in 30〜40 runs. Simulated mass numbers of positively and negatively charged fragments for lignin monomer and dimer showed considerably good accordance with the experimental results in TOF-SIMS observed by Saito and co-workers.), (3)Fragments Distribution of Thermal Decomposition for PS and PET with QMD Calculations by Considering the Excited and Charged Model Molecules(Simulations by a quantum molecular dynamics(QMD) (MD with MO) method were demonstrated on the thermal decomposition of PS and PET polymers using the model molecules at the ground state including excited and positive charged states. The calculated neutral, positive and negative fragment distributions of PS and PET models with 0.82 eV energy control were obtained as (93.5, 2.3, and 4.3%), and(87.8, 5.3, and 6.9%) to the total fragments, respectively. The ratios seem to correspond well to the values observed experimentally in SIMS.). Less

我们从（A）与时间无关和（B）与时间相关的哈密顿量两种理论观点出发，考虑了理论表面光谱仪器的发展，以便通过表面科学仪器模拟物质的电子光谱，并获得质谱分别通过MS和静态或TOF SIMS。在（A）中，按以下方式进行六种光谱分析（1）O-、CO-、的X射线光电子和碳Kα发射测量和计算；含 N 和 S 物质（对 PEO、PVA、PVME、PVMK、PET、P4VP、PAO、PPS 聚合物的化合价 XPS 和碳 Ka XES 进行组合分析，以确定 pσ- 和 pπ- 的单独贡献我们使用模拟的 Cls 光电子和 C 计算了模型分子的所有 CEBE。 Kα 发射光谱与我们的测量结果非常吻合。），（2）Mn_12 分子磁体的电子结构：理论与实验，（3）乙烯和苯分子的共振 X 射线发射光谱的模拟（我们提出了(4)以单一构型近似为中间态的从头算MO计算的俄歇电子能谱理论分析。含第二周期元素的物质（使用模型分子通过 DFT 计算对四种物质 [石墨、GaN、SiO_2、LiF] 进行的模拟 AES 和价态 XES 与实验结果相当一致。物质的实验 AES 分为各个范围C、N、0 和 F KVV' 光谱分别为 1s-2s2s、1s-2s2p 和 1s-2p2p 跃迁。） (5)壳聚糖热分解过程的XPS能谱模拟 (6)碳同素异形体的X射线光电子能谱分析（我们使用阿姆斯特丹密度泛函（ADF）程序进行DFT计算，模拟碳同素异形体（金刚石、我们首先描述了价电子谱的模拟方法来区分石墨、单壁碳纳米管（SWCN）和富勒烯C_60）。从石墨碳中分离出碳的金刚石相，然后根据计算出的模型分子的核心电子结合能（CEBE）之间的差异评估WD值（使用ΔE_ks方法（如MO中的ΔSCF方法））和碳同素异形体的实验 CEBE 碳同素异形体的 WD 值对应于从精确圆柱获得的功函数的实验值顺序 (CNT < 石墨 < 金刚石 < C_<60>)。（1）量子分子动力学方法模拟碳同素异形体分子的热分解（为了模拟碳同素异形体分子的热分解[单壁碳纳米管（SWNT）模型{arm-chair(C_<54>H_<12>) ), zigzag(C_<50>H_<10>) 类型)、C_<60> 和图形模型 C_<42>H_<16>]，我们使用 MD 和半经验 AM1 MO 方法（一种 QMD）。） (2)采用QMD方法对热分解假设下的木质素单体和二聚体进行SIMS模拟(木质素单体和二聚体的热分解已采用量子分子动力学（DMD）方法进行模拟，通过SCF MO计算得到最后一个MD步骤的每个数据的热分解碎片，并模拟了单体和二聚体木质素的碎片分布。木质素单体和二聚体的带正电荷和负电荷片段的模拟质量数与 Saito 及其同事观察到的 TOF-SIMS 实验结果非常一致。） (3)考虑激发和带电模型分子的 QMD 计算对 PS 和 PET 热分解的碎片分布（Simulations by a Quantum molecular Dynamics (QMD) (MD with MO) method shown were on the heat精神分析 PS 和 PET 聚合物使用包括激发态和正电荷态在内的基态模型分子，计算得到 0.82 eV 能量控制下的 PS 和 PET 模型的中性、正负片段分布。（93.5%、2.3% 和 4.3%）、和（87.8%、5.3% 和 6.9%），这些比率似乎与 SIMS 中实验观察到的值很好地对应。）。

项目成果

期刊论文数量（0）

专著数量（0）

科研奖励数量（0）

会议论文数量（0）

专利数量（0）

Immobilization of sodium ions on the pore surface of a porous coordination polymer

DOI：
10.1021/ja0606879
发表时间：
2006-04-05
期刊：
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
影响因子：
15
作者：
Horike, S;Matsuda, R;Kitagawa, S
通讯作者：
Kitagawa, S

Fragment distribution of thermal decomposition for lignin monomer by QMD calculations using the excited and charged model molecules

使用激发和带电模型分子通过 QMD 计算木质素单体热分解的碎片分布

DOI：
发表时间：
2008
期刊：
Applied Surface Science 255
影响因子：
0
作者：
Kazunaka Endo;Daisuke Matsumoto;Kenichi Kato;Yusuke Takagi;Tomonori Ida;Motohiro Mizuno;Kaori Saito;Kazuhiko Fukushima;and Nobuhiko Kato
通讯作者：
and Nobuhiko Kato

Simulation of resonant X-ray emission spectra of ethylene and benzene molecules

乙烯和苯分子的共振X射线发射光谱模拟