分子结构振动固有频率与链烷烃热力学性质的定量关系

用分子结构固有频率和分子中的甲基数作为分子结构信息指数,建立链烷烃分子结构与热力学性质的双参数QSPR模型.该模型用于18种链烷烃分子的标准生成焓、标准熵和标准生成自由能实验值的回归分析,得到相关程度大于0.999的标准生成焓、标准熵回归方程和相关程度大于0.99的标准生成自由能回归方程.所得方程用于67种链烷烃的标准生成焓、标准熵和标准生成自由能预测,结果与实验值的相关程度均大于0.9950.  

双原子分子电子光谱的振动结构分析

从电子振转能级的光谱项出发,分析了双原子分子电子振动谱带序和电子振动谱带列的规律,并归纳出德兰德斯表(Deslandres table)及其主要性质.以C2分子电子振动光谱的斯簧谱带系作为实例,说明了如何对电子振动光谱的测量值进行标识,并将它们按振动结构规律整理成德兰德斯表,从而获得有关分子光谱不同态的非谐性常数、振动频率等重要参数以及任意谱带的波数公式.  

MgF2：V^2＋晶体能级和振动结构的DV—Xa研究

首次用DV-X_a方法计算了终端声子激光晶体MgF_2:V~(2+)的电子能级和振动结构,给出的晶场能级与实验值相当接近.使用晶格振动的“呼吸”模型,得到了基态~4B_(1g)和第一激发态~4B_(2g)的振动势能曲线.在简谐振动近似下,它们分别具有454cm~(-1)和460cm~(-1)的声子能量,与实验值399cm~(-1)符合很好.另外,还获得晶体振动的黄昆参数,激活能,和Franck—Condon交距等参数.计算了四种温度(0K,2K,77K和300K)下的振动线形,并与2K的实验吸收谱作了比较.  

Group-theoretical investigation of the tunneling splitting patterns of enolic acetylacetone

Extensive experimental and theoretical studies for enolic acetylacetone have been presented in the literature, but studies of the tunneling splitting patterns are still lacking. In this work we adopt the C_s symmetry equilibrium structure and apply a group-theoretical formalism to study the tunneling splitting pattern of the ground vibrational level of enolic acetylacetone. Enolic acetylacetone has three large-amplitude motions, one intramolecular hydrogen transfer and two methyl torsions. Therefore, the C_s structure of enolic acetylacetone has 18 (3 × 3 × 2) equivalent equilibrium molecular frameworks, nine (3 × 3) of them are from the two methyl torsions, and two are from the intramolecular hydrogen transfer. Tunneling motions among the 18 equivalent molecular frameworks split the ground vibrational level into eight sublevels: A₁, A₄, E₁, E₂, E₃, E₄, G(1) and G(2). In enolic acetylacetone the intramolecular hydrogen transfer induces a rearrangement of the CC, CO single and double bonds, and then triggers two additional 60° internal rotations, one in each of the two methyl groups attached to the hydrogen-bonded malonaldehyde ring. This interaction further complicates the tunneling splitting patterns and increases the difficulty of spectral analysis. In this work the influence of the intramolecular hydrogen transfer on the energy order of the eight sublevels is determined by a group-theoretical formalism.  

Eigenvalues of structures with uncertain elastic boundary restraints

The eigenvalue problems of structures with random elastic boundary supports are studied in this paper. Using the perturbation method, the differential equations including stochastic distributed parameters and random boundary conditions that govern the eigenproblems are transformed to a series of deterministic differential equations and boundary conditions. Then the differential equations and boundary conditions are discretized utilizing the finite element method (FEM). This process is easy to be implemented since the resulting perturbation equations with different orders own the same FEM meshes. The first-order and second-order sensitivities of eigenvalues are derived through solving the deterministic algebraic equations. Upon determining these sensitivities of eigenvalues, the approximate statistic expressions of random eigenvalues considering uncertain elastic boundary supports are established. At the end, several numerical examples are given to illustrate the application and effectiveness of the present method. Comparison of the present numerical results with those from the Monte-Carlo simulation method verifies the accuracy of the developed method.  

Vibrational and rotational analyses of bands between 636 and 660 nm in the red system of CuCl2

The long wavelength end of the electronic spectrum of CuCl₂, between 636 and 660 nm, has been recorded in the gas phase by laser-excitation spectroscopy using a sample prepared at low temperatures (ca. 10 K) in a free-jet expansion. Under these conditions, it is possible to resolve vibrational, rotational, and even Cu hyperfine structure. The (0, 0) band of the E²Π_u-X²Π_g transition has been identified with an origin at 15546.286(3) cm⁻¹ for ⁶³Cu³⁵Cl₂. The observation and analysis of bands involving vibrationally excited levels has allowed the determination of all three vibrational intervals for the E²Π_u state (ν₁ = 335.88 cm⁻¹, ν₂ = 112.42 cm⁻¹, and ν₃ = 482.17 cm⁻¹, ⁶³Cu³⁵Cl₂). In addition, two other, unrelated transitions have been identified in the same narrow wavelength region. This, combined with the observation of local perturbations of the rotational structure in various bands, reveals the presence of other closely lying electronic states in the same energy region.  

Mode-selective internal conversion of perylene

We observed fluorescence excitation spectra and dispersed fluorescence spectra for single vibronic level excitation of jet-cooled perylene-h ₁₂ and perylene-d ₁₂, and carefully examined the vibrational structures of the S₀ ¹ A _g and S₁ ¹ B _2u states. We performed vibronic assignments on the basis of the results of ab initio calculation, and found that the vibrational energies in the S₁ state are very similar to those in the S₀ state, indicating that the potential energy curves are not changed much upon electronic excitation. We conclude that the small structural change is the main cause of its slow radiationless transition and high fluorescence quantum yield at the zero-vibrational level in the S₁ state. It has been already reported that the lifetime of perylene is remarkably short at specific vibrational levels in the S₁ state. Here, we show that the mode-selective nonradiative process is internal conversion (IC) to the S₀ state, and the ν₁₆(a _g ) in-plane ring deforming vibration is the promoting (doorway) mode in the S₁ state which enhances vibronic coupling with the high-vibrational level (b _2u ) of the S₀ state.  

任意边界板结构的声辐射模态误差传感器的设计

获取声辐射模态伴随系数是基于声辐射模态理论进行主动结构声控制(ASAC)的重要环节。以往PVDF分布式传感器的设计难点是振速展开受边界条件的限制,其设计过程往往是针对特定边界条件展开的。本文在声辐射模态理论和两维分布式传感器的压电方程的基础上,将板表面振速分布用Legendre多项式展开,给出了两维板结构的PVDF传感器形状与边界条件无关的设计方法。这样设计得到的传感器能应用于任意边界条件和任意振速分布的两维板结构,且实时性好,拓宽了其应用范围。本文还分别以固定边界条件板及在该板中任取一小区域两种情况为例,证明了该设计方法的可行性。  

Comparison of Theoretical Methods and Basis Sets for ab initio and DFT Calculations of the Structure and Frequencies of Normal Vibrations of Polyatomic Molecules

The dependence of the quality of calculation of the geometric parameters and frequencies of normal vibrations on the choice of the theoretical method and the basis set of Gaussian functions has been investigated within the framework of four approximations (DFT/B3LYP, HF, MP2, MP3), using benzene and s-triazine molecules as an example. It has been shown that the molecular parameters calculated using the basis set without polarization functions within the framework of any of the above theoretical methods agree poorly with the experimental data. It has been concluded that the use of the basis set 6-31G(d) within the framework of these methods with allowance for the electron correlation for calculating the geometric parameters and frequencies of normal vibrations of polyatomic cyclic compounds is most optimum in terms of the relation between the expenditure of time and the quality of the calculation. The coefficients of linear scaling of frequencies have been obtained by the DFT/B3LYP method for 22 basis sets that were tested on porphin, pyrrole, indene, and pyridine molecules. Atypically large errors in determining the frequencies of some benzene and s-triazine vibrations have been obtained in a number of quantum-mechanical calculations with large basis sets. The changes in the force field for these cases have been investigated with the example of the benzene molecule.