DEVELOPMENT OF THEORETICAL SURFACE SPECTRAL APPARATUS

为了用表面科学仪器模拟物质的电子能谱，并分别用MS和静态或TOF西姆斯获得质谱，我们从（A）与时间无关和（B）与时间相关的哈密顿量两个理论观点出发，研制了表面光谱理论装置。（1）含O-、CO-、N-和S物质的X射线光电子和碳Kα发射测量和计算（对PEO、PVA、PVME、PVMK、PET、P4 VP、PAO、PPS聚合物进行价态XPS和碳K α XES的组合分析以确定pσ-、用密度泛函理论计算了聚合物的pπ键分子轨道。我们用Δ Eks方法计算了模型分子的所有CEBE。计算得到的Cl_s光电子谱和C_K_α发射谱与我们的测量结果符合得很好。（2）Mn_（12）分子的电子结构 ...更多信息 磁铁：（3）乙烯和苯分子共振X射线发射光谱的模拟（我们提出了一种以单组态近似为中间态的从头算分子轨道计算分析共振X射线发射光谱的理论方法）。（4）含第二周期元素物质的俄歇电子能谱的理论分析（用模型分子DFT计算石墨、GaN、SiO_2、LiF四种物质的AES和价态XES的模拟结果与实验结果符合得相当好。对C、N、0和F-KVV '谱的1 s-2s 2s、1 s-2s 2 p和1 s-2 p2p跃迁范围内的实验AES进行了分类。 （5）壳聚糖热分解过程的XPS光谱模拟（6）碳同素异形体的X射线光电子能谱分析（我们使用Amsterdam密度泛函（ADF）程序进行DFT计算，以模拟碳同素异形体（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）。本文首先介绍了区分碳的金刚石相和石墨相的价电子能谱模拟方法，然后根据碳的同素异形体的芯电子结合能（CEBE）的计算值（用Δ Eks方法（类似于MO中的ΔSCF方法））与实验值之间的差异来评价WD值。碳同素异形体的WD值对应于<60>后藤及其同事从精确的圆柱形分析器（CMA）检测器获得的功函数的实验值的顺序（CNT &lt;石墨&lt;金刚石&lt; C_）。在（B）中，进行了如下三项研究：（1）通过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（扶手椅（C_<54>H_<12>）、锯齿形（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AM 1 MO方法（一种QMD）。（2）采用量子分子动力学（QMD）方法模拟了木质素单体和二聚体的热分解西姆斯。在最后一步分子动力学计算的每个数据上，我们得到了热分解产物的正、中性和负变化片段，并模拟了30 ~ 40次最后一步分子动力学计算中木质素单体和二聚体的片段分布。模拟的木质素单体和二聚体的正电荷和负电荷片段的质量数与Saito等人在TOF-SIMS中观察到的实验结果相当一致。（3）考虑激发态和荷电态模型分子的量子分子动力学（QMD）方法模拟PS和PET聚合物的热分解碎片分布（使用基态包括激发态和荷电态的模型分子，通过量子分子动力学（QMD）（MD with MO）方法模拟PS和PET聚合物的热分解。在0.82 eV能量控制下，PS和PET模型的中性、正性和负性碎片分布分别占总碎片的93.5%、2.3%和4.3%以及87.8%、5.3%和6.9%。该比率似乎与在西姆斯中实验观察到的值很好地对应。少

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