DEVELOPMENT OF THEORETICAL SURFACE SPECTRAL APPARATUS

理论表面光谱仪的研制

• 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

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

为了用表面科学仪器模拟物质的电子光谱，并用MS和静态或飞行时间质谱仪分别获得物质的质谱图，我们从两个理论角度考虑了理论表面光谱仪器的发展：(A)独立于时间和(B)依赖于时间的哈密顿量。(1)含O-、CO-、N-和S的物质的X-射线光电子能谱和碳-Kα发射的测量和计算(结合价态XPS和碳Ka-XES对PEO、PVA、PVME、PVMK、PET、P4VP、PAO、PPS聚合物进行了分析，通过密度泛函理论计算确定了聚合物的p-σ-和p-π-键各自的贡献。我们用ΔE_ks方法计算了所有模型分子的CEBE。我们模拟的ClS光电子和C-K-α发射光谱与我们的测量结果符合得很好。)，(2)一个Mn_12分子…的电子结构更多磁体：理论和实验，(3)模拟乙烯和苯分子的共振X射线发射光谱(我们提出了一种用单组态近似作为中间态从头算计算共振X射线发射光谱的理论方法)。(4)用模型分子密度泛函理论计算含第二周期元素的物质(模拟的四种物质[石墨、GaN、SiO_2、LiF]的俄歇电子能谱和价态XES)，与实验结果吻合较好。(5)壳聚糖在热分解过程中的XPS光谱模拟(6)碳同素异形体(金刚石、石墨、单壁碳纳米管(SWCN)和富勒烯C_(60))的X射线光电子能谱分析。我们首先介绍了区分碳的金刚石相和石墨碳的价电子光谱的模拟方法，然后用ΔE_k方法(如分子轨道中的Δ自洽场方法)计算了模型分子的核-电子结合能(CEBE)和实验的碳同素异形体的核-电子结合能(CEBE)的差值，进而估算了WD值。碳同素异构体的WD值对应于Goto‘s和他的同事从精密圆柱形分析仪探测器获得的功函数的实验值的顺序(CNT和lt；石墨和lt；钻石和lt；C&lt；60和gt；)在(B)中，进行了如下三项研究：(1)用量子分子动力学方法模拟碳同素异构体分子的热分解(为了模拟碳同素异构体分子的热分解[单壁碳nanotube(SWNT)models{arm-chair(C_&lt；54&gt；H_&lt；12&gt；)、Zigzag(C_&lt；50&gt；H_&lt；10&gt；)、C_&lt；60&gt；和图形模型C_&lt；42&gt；H_&lt；16&gt；]，我们使用分子动力学和半经验AM1分子轨道方法(一种QMD)对木质素单体和二聚体的SIMS进行了模拟。通过SCF分子轨道计算，得到了分子动力学最后一步的每一步数据中具有正变化、神经变化和负变化的热分解碎片，并模拟了最后一步木质素单体和二聚体木质素在30~40次循环中的碎片分布。模拟的木质素单体和二聚体的正负电荷碎片的质量数与在TOF-SIMS中观察到的实验结果很好地一致。)，(3)考虑激发态和带电的模型分子，用QMD计算了PS和PET的热分解碎片分布(用量子分子动力学(MD With MO)方法模拟了PS和PET聚合物的热分解过程)。计算得到能量控制为0.82 eV的PS和PET模型的中性碎片、正碎片和负碎片分布分别为93.5、2.3和4.3%，占碎片总数的87.8、5.3和6.9%。这些比率似乎与在模拟人生实验中观察到的值很好地一致。较少

项目成果

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

• 发表时间: 2008
• 期刊: Applied Surface Science 255
• 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

Electronic structure of a Mn 12 molecular magnet: Theory and experiment

• DOI: 10.1103/physrevb.75.014419
• 发表时间: 2007-01
• 期刊: Physical Review B
• 影响因子: 3.7
• 作者: D. Boukhvalov;M. Al-Saqer;E. Kurmaev;A. Moewes;V. Galakhov;L. D. Finkelstein;S. Chiuzbăian;M. Neumann;V. Dobrovitski;M. Katsnelson;M. Katsnelson;A. Lichtenstein;A. Lichtenstein;B. Harmon;K. Endo;J. North;N. Dalal

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

• 发表时间: 2006
• 期刊: Chem. Phys. Lett 426
• 作者: T. Ida;N. Kato;D. Matsumoto;M. Mizuno;K. Endo
• 通讯作者: K. Endo

XPS Spectral Simulation of Chitosan in Thermal Decomposition Process

壳聚糖热分解过程的XPS光谱模拟

• 发表时间: 2007
• 作者: 遠藤一央;他
• 通讯作者: 他