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 SIMS获得物质的质谱，我们从(A)时间无关和(B)时间相关的理论角度考虑了理论表面谱仪的开发。在(A)中，六种光谱分析方法如下：(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(通过DFT计算，对PEO、PVA、PVME、PVMK、PET、P4VP、PAO、PPS聚合物的价态XPS和碳k - x进行了组合分析，确定了聚合物的pσ-和π-键成键分子轨道的单独贡献。我们使用ΔE_ks方法计算了模型分子的所有cebe。(2) Mn_12分子的电子结构。More磁体：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（我们提出了一种用单构型近似作为中间态从从头算MO计算中分析共振x射线发射光谱的理论方法。）(4)利用模型分子进行DFT计算，对含第二周期元素物质的俄俄电子能谱（模拟AES和四种物质[石墨，GaN, SiO_2， LiF]的价态XES）进行了理论分析，结果与实验结果吻合较好。(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(我们使用阿姆斯特丹密度泛函数（ADF）程序进行DFT计算，模拟了碳同素异形体(金刚石、石墨、单壁碳纳米管（SWCN）、和富勒烯C_60)。我们首先描述了用价电子能谱模拟方法来区分碳的金刚石相和石墨相，然后利用模型分子计算的核心电子结合能（CEBE）s(使用ΔE_ks方法（类似于MO中的ΔSCF方法）与碳同素异形体的实验CEBE之间的差异来评估WD值。碳同素异形体的WD值对应于Goto等人用精确圆柱分析仪（CMA）探测器得到的功函数的实验值顺序（CNT <石墨<金刚石< C_<60>）。在(B)中，进行了以下三项调查；（1)利用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>）、之形（C_<50>H_<10>）类型）、C_<60>和图形模型C_<42>H_<16>]，我们采用半经验AM1 MO方法（QMD的一种）进行MD。）(2)采用QMD方法模拟木质素单体和二聚体在热分解假设下的SIMS（采用量子分子动力学（DMD）方法模拟木质素单体和二聚体的热分解过程）。在最后一步的SCF MO计算中，我们得到了正、神经和负变化的热分解片段，并在30 ~ 40次运行中模拟了最后一步的单体和二聚木质素的片段分布。模拟木质素单体和二聚体的带正电荷和带负电荷片段的质量数与Saito及其同事在TOF-SIMS中观察到的实验结果相当吻合)。(3)考虑激发态和带电荷模型分子的PS和PET热分解碎片分布(利用量子分子动力学（QMD） （MD with MO）方法对PS和PET聚合物在基态（包括激发态和带正电态）下的热分解进行了模拟。在0.82 eV能量控制下，计算得到PS和PET模型中性、正、负碎片占总碎片的比例分别为（93.5、2.3、4.3%）、（87.8、5.3、6.9%）。这些比率似乎与SIMS实验中观察到的值很吻合。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