X-ray Atomic Orbital and Molecular Orbital Analyzes

一个最小二乘法结合正交轨道函数之间的关系制定。这等价于整数个电子（小于2）占据轨道的幂等性条件。本研究的第一个目的是通过分析X射线衍射法测得的电子密度分布（EDD）来获得原子轨道（AO）或分子轨道（MO）。第二个目标是精确地测量结构因子，以便可靠地获得重原子（如稀土元素）组成的晶体中的EDD.成功地应用最小二乘法，得到了Cu^<2+>在低对称场中的3d轨道函数.因此，可以通过X射线结构因子分析来获得AO。我们称这种方法为X射线AO分析。类似的研究，以获得MO，这是所谓的X射线MO分析，仍在研究中，因为意想不到的长计算时间是必要的。然而 ...更多信息 解决了以下三个基本问题，实现了X射线MO分析。首先，在简单的有机化合物中，双中心电子的散射因子大于它们的实验误差，对于许多反射足以进行最小二乘分析。其次，成功地制定了双中心电子的温度因子，给出了合理的R因子。第三，找到了适合于X射线分子轨道分析的基本高斯型函数，大大降低了原子核附近电子密度的不一致性，随着X射线电子衍射分析的发展，对测量精度提出了更高的要求。发现多重衍射效应是如此频繁地出现，以致于它引起的强度扰动很容易超过PtP_2晶体结构因子的1%。因此，在用4圆衍射仪测量期间避免了它。在牛津低温恒温器的冷氮气流的稳定温度区也测量了强度。这些改进是在本研究中实现的。在165K下，用X射线衍射分析法测量了CeB_6中4f电子密度的分布，并根据晶场理论进行了分析。据我们所知，这是第一次成功地对f电子进行定量分析。重原子晶体的电子衍射研究取得了显著进展。少

A least-squares method incorporating orthonormal relationships between orbital functions were formulated. This is equivalent to the idempotency condition for orbitals occupied by integer number, which is less than 2, of electrons. The first aim of the present research is to obtain atomic orbitals (AO) or molecular orbitals (MO) by analyzing electron density distribution (EDD) measured by X-ray diffraction method with this method. The second aim is to measure so accurate structure factors that EDD in crystals composed of heavy atoms such as rare-earth elements can be obtained reliably.The least-squares method was successfully applied aand 3d-orbital functions of Cu^<2+> in a low symmetry field were obtained. Therefore AO can be obtained by the analysis of X-ray structure factors. We call the method as X-ray AO analysis. The similar research for obtaining MO,which is called as X-ray MO analysis, is still being investigated because unexpectedly long computation time is necessary. However … More following three basic problems has been solved and it is feasible to accomplish X-ray MO analysis. First, in a simple organic compounds scattering factors of two-center electrons is larger than their experimental error for many reflections enough for the least-squares analysis. Second, ttemperature factors for two-center electrons are successfully formulated, giving reasonable R-factors. Third basic Gaussian-type functions which is proper for X-ray MO analysis was found, which reduce the inconsistency of electron density near atomic nuclei significantly.As X-ray analysis of EDD develops more accurate measurement is required. Multiple diffraction effect was found to occur so frequently that intensity perturbations due to it easily exceeded 1% of measured structure factors for PtP_2 crystals. Therefore it was avoided during the measurement with a 4 cirde diffractometer. Intensities were also measured in stable temperature region of toold nitrogen gas stream of the Oxford cryostat. These improvementts were achieved in the present research. As s result of it 4f-electron density distribution in CeB_6 was measured clearly at 165K and it was analyzed based on the crystal field theory by X-ray AO analysis. This to our knowledge is the first successful quantitative analysis of felectrons. The studies on EDD in crystals composed of heavy atoms showed a remarkable progress. Less