分子诱导效应指数与链烷烃的沸点

利用基团的诱导效应指数，首次提出了分子的诱导效应指数的概念，并定义了 链烷烃的有效碳链长度NC＝（MIs,N/MIb,N)·N，式中MIs,N,MIb,N分别为直链和支 链异构体的分子诱导效应指数。研究结果表明，链烷烃的沸点Tb(℃）与NC关系是 ：1n(806.5-Tb)=6.9824-0.11431NC^2/3     

人血清与头发中铜,锌,铁,钙,镁,锰含量的相关分析

平行测定了５４例（男３１例，女２３例）成人血清和头发中铜，锌，铁，钙，镁和锰的含量，相关分析结果表明，血清与头发中６种元素的不相关两类样品比较，血清测定方法简便，误差小，但在检测人体内元素含量水平时，头发的测量结果比血清更灵敏。     

Scaling in second-order electron correlation calculations using systematic sequences of even-tempered basis sets

Improved results can often be obtained from second-order Rayleigh-Schrödinger perturbation calculations of electron correlation energies using large basis sets by introducing a scaling factor in the zero-order Hamiltonian. The scaling parameter may be determined from full third-order calculations using a smaller basis set. This scaling procedure can be applied in a systematic fashion by employing a sequence of even-tempered basis sets. Calculations illustrating this approach for the beryllium atom and the neon atom are presented. The scaling procedure is also employed in conjunction with a universal systematic sequence of basis functions. Calculations illustrating this Correlation energy — Mang-body perturbation theory.Work supported in part by S.R.C. Research Grant GR/B/4738.6.S.R.C. Advanced Fellow.     

Multiplex amplified product-length polymorphism analysis of 36 mitochondrial single-nucleotide polymorphisms for haplogrouping of East Asian populations

We present a reliable, rapid, and economical multiplex amplified product-length polymorphism (APLP) method for analyzing the haplogroup-diagnostic mitochondrial single-nucleotide polymorphisms (mtSNPs) in East Asian populations. By examining only 36 haplogroup-specific mtSNPs in the coding region by using four 9-multiplex polymerase chain reaction (PCR) and subsequent electrophoresis, we could safely assign 1815 individuals from 8 populations of Japanese, Korean, Chinese, and Germans to 45 relevant haplogroups. This multiplex APLP analysis of coding-region mtSNPs for haplogrouping is especially useful not only for molecular phylogenetic studies but also for large-scale association studies due to its rapid and economical nature. This is the first panel of mtSNPs in the coding region to be used for haplogrouping of East Asian populations.     

A two-dimensional infrared correlation spectroscopic study on the thermal degradation of poly(2-hydroxyethyl acrylate)-co-methyl methacrylate/SiO2 nanohybrids

Two-dimensional infrared (2D IR) correlation spectroscopy was applied to study the structural changes occurring in the decomposition of PHEA-co-MMA/SiO₂. Complicated absorption spectral changes were observed in the heating process. 2D IR analysis indicates that during heating, covalent bonds, (Si-O-C), between the polymer and the inorganic moiety were formed, which was the main factor in the improvement in thermal properties of the hybrids such as the decomposition temperatures (T_d). The thermal stability of the hybrids was also studied by solid-state ²⁹Si MAS NMR spectroscopy and TGA tests. Their results complemented each other well.     

采用多光程长建模方法检测血液成分含量

为了提高近红外光谱血液成分含量分析模型的预测精度,利用多个光程长(optical path length,OPL)共同参与建模的方法进行血糖等6种血液成分的定量分析。通过微米位移机构实现不同光程长血液光谱的测量,由全自动生化分析仪给出生化成分分析结果,并出具化验单。采用偏最小二乘法(PLS2)进行血液的近红外光谱建模及预测。由于血液光谱存在显著的非线性特征,不同光程长的血液样本的等效吸收系数不同,同一波长不同光程长(0.20~1.25 mm)测得的血液光谱互不相关。主动把非线性特性作为一种测量手段引入,不再利用单个的最佳光程长建模,而是用各个血液组分对应的多个最佳光程长的近红外光谱同时参与建立校正模型,进行血液成分的分析预测。研究结果表明,多光程长建模方法用于血液成分含量分析,可提高血液成分校正模型的预测精度。     

Møller-Plesset (MP2) perturbation theory for large molecules

Summary A novel formulation of MP2 theory is presented which starts from the Laplace transform MP2 ansatz, and subsequently moves from a molecular orbital (MO) representation to an atomic orbital (AO) representation. Consequently, the new formulation is denoted AO-MP2. As in traditional MP2 approaches electron repulsion integrals still need to be transformed. Strict bounds on the individual MP2 energy contribution of each intermediate four-index quantity allow to screen off numerically insignificant integrals with a single threshold parameter. Implicit in our formulation is a bound to two-particle density matrix elements. For small molecules the computational cost for AO-MP2 calculations is about a factor of 100 higher than for traditional MO-based approaches, but due to screening the computational effort in larger systems will only grow with the fourth power of the size of the system (or less) as is demonstrated both in theory and in application. MP2 calculations on (non-metallic) crystalline systems seem to be a feasible extension of the Laplace transform approach. In large molecules the AO-MP2 ansatz allows massively parallel MP2 calculations without input/output of four-index quantities provided that each processor has in-core memory for a limited number of two-index quantities. Energy gradient formulas for the AO-MP2 approach are derived.Dedicated to Prof. W. Kutzelnigg whose books on theoretical chemistry aroused my interest in this field     

Spectrum analysis of U-doped LaBr3 single crystals. Part 1: crystal-field analysis

Single crystals of U³⁺:LaBr₃ were grown by the Bridgman-Stockbarger technique. High-resolution polarized absorption spectra of the crystals were recorded at 4.2 K in the 4000-50,000 cm⁻¹ range. Sixty-four experimental crystal-field energy levels of the U³⁺ ion were fitted to a semiempirical Hamiltonian employing free-ion, one-electron crystal-field as well as two-particle correlation crystal-field (CCF) operators with an r.m.s. deviation of 28 cm⁻¹. The performed analysis of the spectra enabled the determination of crystal-field parameters and assignment of the observed 5f³→5f³ transitions. The effects of selected CCF operators on the splitting of some specific U³⁺ multiplets have been investigated and the obtained values of Hamiltonian parameters are discussed and compared with those reported in previous analyses.     

Influence of Urbach Energy,Temperature, and Longitudinal Position in the Active Layer on Carrier Diffusion Length in Perovskite Solar Cells

The diffusion length of charge carriers in the active layer of a perovskite solar cell (PSC) of the structure Glass/PEDOT: PSS/CH₃NH₃PbI₃/PC60BM/Al is modelled. It is found that the diffusion length depends on the position x in the active layer measured from the PEDOT: PSS interface, Urbach energy and temperature. By varying the voltage in the range from zero to , it is shown that the dependence of diffusion length on the position x in the active layer reduces at higher voltage. The combined influence of applied voltage and temperature on the diffusion length of charge carriers is investigated and it is found that in the low voltage range the diffusion length is temperature independent, but it becomes significantly temperature dependent at higher voltages. Also, it is found that the diffusion length decreases as the applied voltage increases and this reduction becomes much more significant at higher voltage and temperatures. The combined influence of applied voltage and Urbach energy on diffusion length of charge carriers reveals that the diffusion length decreases when both the applied voltage and Urbach energy increase. However, the reduction in the diffusion length due to the increase in Urbach energy becomes less significant at higher voltage.     

Theoretical investigation of excited states of molecules. An application on the nitrogen molecule

Diverse existing lines for the calculation of excited states are exposed, with an emphasis on those methods that consider both types of correlation energy: the dynamic and the non-dynamic one. We analyze the possibility of to calculate the dynamic correlation energy using a correlation energy density functional applied to a multi-determinantal wavefunction, which would include the non-dynamic correlation energy, versus the use of mono-determinantal wavefunctions, which are not able to include the long-range correlation energy, and versus the use of variational or perturbative calculations from multi-determinantal wavefunctions, with their excessive computational cost. The results obtained with several methods are compared. Contribution to the Serafin Fraga Memorial Issue.