基于最终类集的复杂样本设计研究

本文依据最终类集样本可以近似均等选择概率下各种多阶段抽样设计样本的理论,构建出多阶段抽样下复杂样本设计的理论分析框架,解析出影响复杂样本估计量设计效应的两个基本因素:最终类集同质系数和最终类集规模,分析了它们对复杂样本估计量设计效应的影响机理及相互作用机制,并应用于我国一体化住户调查的主样本设计。     

Bounds on partial derivatives of NURBS surfaces

In this paper, we estimate the partial derivative bounds for Non-Uniform Rational B-spline(NURBS) surfaces. Firstly, based on the formula of translating the product into sum of B-spline functions, discrete B-spline theory and Dir function, some derivative bounds on NURBS curves are provided. Then, the derivative bounds on the magnitudes of NURBS surfaces are proposed by regarding a rational surface as the locus of a rational curve. Finally, some numerical examples are provided to elucidate how tight the bounds are.     

Determination of Volatile Organic Compounds by a Novel Polymer Spin-Coated Thin Film and Surface Plasmon Resonance

Here, the synthesis, characterization, and volatile organic compound (VOCs) sensing of a 1,3-dimethyl polyphenylene vinylene polymer is reported. The synthesis was performed by a Witting condensation through the reaction of 1,4-terphthaldehyde with the phosphonium chloride of meta-xylene. The material was characterized by infrared spectroscopy, elemental analysis, and thermogravimetric analyses. Thin films of the polymer were prepared by spin coating at speeds from 1000 to 5000?rpm. Ultraviolet–visible spectroscopy and surface plasmon resonance were used to characterize the spin-coated films. The thicknesses of the films were estimated by fitting the curves and were between 4.5 and 24.5?nm depending on the speed. The refractive index of the new polymer was 1.72. The polymer spin-coated films were exposed to volatile organic vapors to characterize their sensing properties by surface plasmon resonance as a function of time. The results showed that the new material responded rapidly, sensitively, and reversibly to VOCs.     

Substituent Effect on the Electronic Properties and Nature of the W≡C Bond in trans‐Cl(OC)(H3P)3W(≡C‐para‐C6H4X) (X = H,F, SiH3, CN,NO2, SiMe3, CMe3, NH2, NMe2) Complexes: A Computational Quantum Chemistry Study

In this investigation, we describe substituent effect on the dipole moment, ionization potential, electron affinity, structure, frontier orbitals energy, in the trans‐Cl(OC)(H₃P)₃W(≡C‐para‐C₆H₄X) (X = H, F, SiH₃, CN, NO₂, SiMe₃, CMe₃, NH₂, NMe₂) complexes using MPW1PW91 quantum chemical calculations. The nature of chemical bond between the [Cl(OC)(H₃P)₃W]⁻ and [C‐para‐C₆H₄X]⁺ fragments was illustrated with energy decomposition analysis (EDA). Percentage composition in terms of the defined groups of frontier orbitals for these complexes was inspected to investigate the character in metal–ligand bonds. Quantum theory of atoms in molecules (QTAIM) was used for illustration of metal–ligand bonds in these complexes.     

Quantum reaction dynamics of C(1D) + HD → CH(CD) + D(H) on the ground state potential energy surface

We present accurate quantum dynamic calculations of the reaction C(¹D) + HD on the latest version of the potential energy surface [Zhang et al., J. Chem. Phys. 140, 234301 (2014)]. Using a Chebyshev real wave packet method with full Coriolis coupling, we obtain the initial state‐specified ( ) reaction probabilities, integral cross sections, and rate constants. The resulting probabilities display oscillatory structures due to numerous long‐lived resonances supported by the deep potential well. The calculated rate constants and CD/CH product branching ratio at room temperature are in reasonably good agreement with the experimental measurements.     

Global X2A′ potential energy surface of Li2H and quantum dynamics of H + Li2 (X1Σg+) → Li + LiH (X1Σ+) reaction

A global potential energy surface (PES) for the electronic ground state of Li₂H system is constructed over a large configuration space. About 30 000 ab initio energy points have been calculated by MRCI‐F12 method with aug‐cc‐pVTZ basis set. The neural network method is applied to fit the PES and the root mean square error of the current PES is only 1.296 meV. The reaction dynamics of the title reaction has been carried out by employing time‐dependent wave packet approach with second order split operator on the new PES. The reaction probability, integral cross section and thermal rate constant are obtained from the dynamics calculation. In most of the collision energy regions, the integral cross sections are in well agreement with the results reported by Gao et al. The rate constant calculated from the new PES increases in the temperature range of present investigation.     

Theoretical Study of Substituent Effects on Geometric and Spectroscopic Parameters (IR, 13C, 29Si NMR) and Energy Decomposition Analysis of the Bonding in Molybdenum Silylidyne Complexes CpMo(CO)2(≡Si‐para‐C6H4X)

In this study, we report the substituent effect on the structures, frontier orbital analysis, and spectroscopic properties (IR , ¹³C , ²⁹Si NMR ) in the molybdenum silylidyne complexes CpMo (CO )₂(≡Si‐para ‐C₆H₄X ) (X = H, F, Cl, CN , NO₂ , Me, OMe , NH₂ , NHMe ) using MPW1PW91 quantum chemical calculations. The calculated structural parameters and spectral parameters are compatible with the experimental values in similar complexes. The nature of the chemical bond between the [Cp(OC ) ₂Mo ]⁻ and [Si‐para ‐C₆H₄X ]⁺ fragments was explored with energy decomposition analysis (EDA ). The percentage composition in terms of the defined groups of frontier orbitals for CpMo (CO )₂(≡Si‐para ‐C₆H₄X ) complexes was investigated to explore the character of the metal–ligand bonds. The linear correlations between the properties and Hammett constants (σ _p) were illustrated. Natural bond orbital analysis (NBO ) was used to illustrate the electronic structure of the complexes.     

Computational studies on optoelectronic and charge transfer properties of some perylene‐based donor‐π‐acceptor systems for dye sensitized solar cell applications

We report DFT studies on some perylene‐based dyes for their electron transfer properties in solar cell applications. The study involves modeling of different donor‐π‐acceptor type sensitizers, with perylene as the donor, furan/pyrrole/thiophene as the π‐bridge and cyanoacrylic group as the acceptor. The effect of different π‐bridges and various substituents on the perylene donor was evaluated in terms of opto‐electronic and photovoltaic parameters such as HOMO‐LUMO energy gap, λ_max, light harvesting efficiency(LHE), electron injection efficiency (Ø_inject), excited state dye potential (E^dye*), reorganization energy(λ), and free energy of dye regeneration (). The effect of various substituents on the dye–I₂ interaction and hence recombination process was also evaluated. We found that the furan‐based dimethylamine derivative exhibits a better balance of the various optical and photovoltaic properties. Finally, we evaluated the overall opto‐electronic and transport parameters of the TiO₂‐dye assembly after anchoring the dyes on the model TiO₂ cluster assembly.     

Solvent effect on the tautomers' stabilities of protonated N,N‐dimethylnitrosamine: The role of hydrogen bonds network

DFT calculations have been applied in order to study the free energies of the structures corresponding to the three different protonation sites of N,N‐dimethylnitrosamine (DMNA). The solvent effect has been taken into account through the study of clusters consisting of protonated DMNA and up to four explicit water molecules, either in the absence or in the presence of a continuum (CPCM) solvation model. Addition of water molecules has been done by a careful screening procedure through which all important hydrogen bonds are likely to be considered. Protonation of DMNA makes all their lone pairs no longer available for hydrogen bond formation with water molecules, such that hydrogen bonds have been observed, for almost all structures, only between water molecules and between one water molecule and the protonated DMNA, in this latter case intermediated by the proton. The stabilities of the solvated structures are governed not only by the number of hydrogen bonds but also by the positions of the water molecules involved in these bonds, as well as by which of them donate or accept H atoms. Our results indicate that oxygen protonation is the most favorable one, regardless of the presence of water molecules. In vacuum protonation at the N‐amino ( 2a ) is approximately as favorable as protonation at the N nitroso ( 2c ). However, in water the former protonation is by far the less favorable one. Our best estimates for the ΔG values in bulk solvent are: ΔG( 2a ) ≈ 17.9, ΔG( 1c ) ≈ 4.3, and ΔG( 2c ) ≈ 4.9 kcal/mol.     

Electrostatic contribution to the ion solvation energy: cavity effects

Ion solvation process has been analysed for the spherically symmetrical system where an ion is located inside a cavity surrounded by an isotropic nonlocal dielectric medium. It has been proven that for any dielectric properties of the medium, the electric field outside the cavity as well as the ion solvation energy depend only on the total ion charge but not of the particular distribution of the ion charge density inside the cavity. These characteristics remain unchanged if the charge is displaced from the external boundary of the cavity into it. Analytical formulas for them have been derived for a particular model of the nonlocal dielectric function. Comparison of results for the solvation energy on the basis of this new theory and of the conventional approach (disregarding the existence of the cavity) shows a significant difference between their predictions if the ion charge is displaced inside the ion cavity.