对称函数各完备集展开系数之间的转换

本文从三种构成完备集的对称函数的定义及有关性质出发，讨论了对称函数在各完备集中展开系数之间的转换，给出了相应的变换矩阵，从而建立了各完备集之间的相互联系.     

镥晶体的绝热量热法测试和热力学函数

文章合成了Lu(NO₃)₃(C₂H₅O₂N)_4.H₂O,用红外和元素分析对其进行了表征。用高精度全自动绝热量热仪,测定了该配合物80-382 K温区的热容, 利用实验热容数据, 根据热容与焓、熵的热力学关系, 求出了配合物85-350 K温区内每隔5 K相对于298.15K的标准热力学函数(HT - H298.15)m和(ST - S298.15)m.在80-350 K温度区间内,配合物的热容随温度升高而增大,没有相转移点和热力学吸收峰的出现,该配合物在此温度区间内是稳定存在的。     

爆破震动信号的小波分析与HHT变换

以实测的爆破震动信号为例,分别应用小波分析和HHT(Hilbert-Huang Transform)变换从不同方面进行对比分析,讨论了爆破震动信号的特征提取和时频分布。结果表明：小波分析和HHT变换都是处理非平稳信号的两种好方法,都能很好地提取信号的主要特征信息和进行滤波、消噪。然而,小波分析存在选择小波基的困难,而HHT变换不需要预先选择基函数,其EMD（empirical mode decomposition）得到的IMF(intrinsic mode function)能反映原始信号的固有特性,通常具有实际物理意义;小波谱的能量在频率范围内分布较宽,而Hilbert能量谱能清晰地表明能量随时频的具体分布,大部分能量都集中在有限的能量谱线上;小波分析中时间、频率分辨率受Heisenberg测不准原理的限制,而HHT变换中时间分辨率不变且精度很高,其频率分辨率则可随信号内在的特性进行自适应调节。分析表明：HHT变换在分析非平稳信号时较小波分析更具适应性,在岩石中波的传播、衰减规律、结构动态响应特征和爆破震动破坏等研究中有着广阔的应用前景。     

改进的移动最小二乘法

近年来发展的无网格方法大多采用移动最小二乘法来构造试函数,而应用移动最小二乘法形成的方程组有时会是病态的甚至奇异的,从而限制了它的发展和应用.本文采用带权正交函数作为基函数对移动最小二乘法做了改进,避免出现病态方程组,且在计算过程中不需要进行矩阵求逆运算,提高了计算速度.之后,借鉴牛顿法、平衡法和摄动法对由移动最小二乘法得到的非线性代数方程组提出了新的求解方法.     

Valence p functions for alkali and alkaline-earth atoms

Contracted Gaussian-type function (CGTF) basis sets are reported for valence p orbitals of the six alkali and alkaline-earth atoms Li, Be, Na, Mg, K, and Ca for molecular applications. These sets are constructed by Roothaan–Hartree–Fock calculations for the ns → np excited states of atoms, in which both linear and nonlinear parameters of CGTFs are variationally optimized. The present CGTF sets reproduce well the numerical Hartree–Fock ns → np excitation energies: the largest error is 0.0009 hartrees for Li. New CGTFs are tested with diatomic Li₂, Na₂, K₂, and MH molecules, where M = Li, Be, Na, Mg, K, and Ca, by self-consistent-field (SCF) and multiconfiguration SCF calculations. The resultant spectroscopic constants compare well with those of more elaborate calculations and are sufficiently close to experimental values, supporting the efficiency of the present set for the valence p orbitals. Received: 9 July 1998 / Accepted: 17 September 1998 / Published online: 1 February 1999     

半胱胺-Zn(Ⅱ)络合反应稳定性及热力学特征研究

采用pH电位滴定法,于温度25℃条件下,获取半胱胺盐酸盐的各级加质子常数(lgK_1~H=10.92,lgK_2~H=8.25)、离解常数(K_(a1)=5.62E-09,K_(a2)=1.20E-11)及其与Zn(Ⅱ)形成配合物的稳定常数(lgk5=36.74)、热力学函数(△rHm=-157.14kJ/mol,△rSm=176.74J/(mol·K),△_rGm=-209.60kJ/mol),并计算各pH条件下半胱胺盐酸盐与Zn(Ⅱ)配合的条件稳定常数。计算得Zn(Ⅱ)与半胱胺盐酸盐配位反应的热力学函数△rGm0、△rHm0、△rSm0,证明反应过程为自发放热。半胱胺盐酸盐与Zn(Ⅱ)形成配合物的稳定常数和条件稳定常数均很大,表明形成的半胱胺锌很稳定。     

环四甲撑四硝胺(HMX)结构和性质的DFT研究

用密度泛函理论(DFT)B3LYP方法,取6-31G基组,求得环四甲撑四硝胺分子的几何构型、电子结构、 IR谱和298～1200 K的热力学性质.全优化几何构型和电子结构均具有Ci对称性.在相邻原子之间以N-NO2键的Mulliken集居数最小,表明其间电子分布较少,预示其为热解和起爆的引发键.IR谱与实验结果良好相符.     

Fourier analysis,correlation functions and nonadiabatic electron transfer: Wavepackets and exact representations

Summary We investigate the validity of several common approximations in the analysis of nonadiabatic intramolecular electron transfer rate constants. Utilizing the Fourier representation of the golden rule form, we study the evolution of the vibrational correlation function that represents the density-of-states-weighted Franck-Condon factor. In particular, we test the validity of the perturbation theoretic golden rule form and of the Gaussian wavepacket representation for the vibrational wavefunctions against numerically exact quantum mechanical propagations. Although specific cases are found in which both of these break down, for a wide range of conditions (including anharmonic behavior and frequency changes), both the Gaussian wavepacket representation and the golden rule are excellent approximations.