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991.
用密度泛函理论优化了三苯甲烷(1)和一系列三(4-硝基苯基)甲烷衍生物2,3和4的几何结构,并计算了其红外光谱和拉曼光谱;通过与实验光谱的对比,对实验光谱中的谱峰进行了指认,并从理论上纠正了部分对3和4红外光谱谱峰不合适的实验指认;同时预测了2,3和4的拉曼光谱.结果表明,几种化合物的振动光谱计算结果与相应的实验结果吻合良好;且化合物2,3和4的拉曼光谱具有相似性. 相似文献
992.
Hossein Nourmohamadi Valeh Aghazadeh Mehdi D. Esrafili 《Surface and interface analysis : SIA》2020,52(3):110-118
Pyrite acts as a catalyst in the mineral processing, and the speed of ferric ion reduction and mineral decomposition increases with increasing cathodic points. In this study, the ferric ion interaction on the (100) and (110) surfaces of pyrite was studied using the density functional theory calculations. The analysis of stability, density of states, and electron density were performed to understand the interaction between the ferric ion and pyrite surfaces. The results showed that pyrite surface is chemically active and tends to absorb ferric ion between two surface sulfur atoms. The hyperconjugation between the 3d orbital of ferric ion and the 3p or 3d orbitals of surface atoms provides the conditions for the Fe3+ ion adsorption. The molecular orbital (MO) and electron density analyses indicate that the 3p orbitals of S atoms play a more important role in bonds formations relative to the 3d orbitals. The (110) surface is more active, and the adsorption energy is larger than that of surface (100), which is the result of decreased cation coordination and the presence of sulfur at the surface. Subsequently, the interaction of the Fe2+ ion, as product of Fe3+ ion reduction and its competitor for adsorption, on the surfaces was studied. The Fe2 + ion adsorbs stronger at the surface of (110), and the adsorption energies at (100) and (110) surfaces were obtained as −24 and −47 kcal/mol, respectively. In general, the Fe3+ ion is a stronger oxidizing agent than Fe2+ on pyrite surfaces. 相似文献
993.
This paper is concerned with the experimental testing and the constitutive modelling of a thermoplastic microcellular polyethylene-terephthalate (MC-PET) foam on the temperature range of 21–210 °C in order to investigate the temperature-dependent performance of the applied parallel viscoelastic-viscoplastic material model. By means of carefully designed uniaxial mechanical tests in temperature chamber, the viscous, elastic and yielding behaviours of the investigated material are identified, which are then applied for selecting suitable viscoelastic-viscoplastic constitutive models. The material characterization process is conducted using finite-element-based fitting method, including also the analysis of the applied numerical optimization algorithm. The fitting results are used to analyse the parameter sensitivity and to propose closed-form analytical relations for the temperature dependency of the material parameters. Finally, the utilisation of the analytical temperature functions for speeding up the parameter-fitting process is also demonstrated. 相似文献
994.
Xiaoyan Cao Liangliang Wu Jun Zhang Michael Dolg 《Journal of computational chemistry》2020,41(4):305-316
Density functional theory has been used to study the biologically important coenzyme NADPH and its oxidized form NADP+. It was found that free NADPH prefers a compact structure in gas phase and exists in more extended geometries in aqueous solution. Ultraviolet–visible absorption spectra in aqueous solution were calculated for NADPH with an explicit treatment of 100 surrounding water molecules in combination with the COSMO solvation model for bulk hydration effects. The obtained spectra using the B3LYP hybrid density functional agree quite well with experimental data. The changes of Gibbs free energies ΔG in reactions of NADPH with O2 observed experimentally in cardiovascular and in chemical systems, that is, NADPH + 2 3O2 → NADP+ + 2 O2− + H+ and NADPH + 1O2 + H+ → NADP+ + H2O2, respectively, were calculated. The NADPH oxidation reaction in the cardiovascular system cannot proceed without activation since the obtained ΔG is positive. The reaction of NADPH in the chemical system with singlet oxygen was found to proceed in two ways, each consisting of two steps, that is, NADPH firstly reacts with 1O2 barrierlessly to form NADP+ and HO2−, from which H2O2 is formed in a spontaneous reaction with H+, or 1O2 and H+ initially form 1HO2+, which further reacts with NADPH to yield NADP+ and H2O2. © 2019 The Authors. Journal of Computational Chemistry published by Wiley Periodicals, Inc. 相似文献
995.
He Ma Wennie Wang Siyoung Kim Man-Hin Cheng Marco Govoni Giulia Galli 《Journal of computational chemistry》2020,41(20):1859-1867
We present PyCDFT, a Python package to compute diabatic states using constrained density functional theory (CDFT). PyCDFT provides an object-oriented, customizable implementation of CDFT, and allows for both single-point self-consistent-field calculations and geometry optimizations. PyCDFT is designed to interface with existing density functional theory (DFT) codes to perform CDFT calculations where constraint potentials are added to the Kohn–Sham Hamiltonian. Here, we demonstrate the use of PyCDFT by performing calculations with a massively parallel first-principles molecular dynamics code, Qbox, and we benchmark its accuracy by computing the electronic coupling between diabatic states for a set of organic molecules. We show that PyCDFT yields results in agreement with existing implementations and is a robust and flexible package for performing CDFT calculations. The program is available at https://dx.doi.org/10.5281/zenodo.3821097 . 相似文献
996.
Evan Walter Clark Spotte-Smith Peiyuan Yu Samuel M. Blau Ravi S. Prasher Anubhav Jain 《Journal of computational chemistry》2020,41(24):2137-2150
Thermal storage and transfer fluids have important applications in industrial, transportation, and domestic settings. Current thermal fluids have relatively low specific heats, often significantly below that of water. However, by introducing a thermochemical reaction to a base fluid, it is possible to enhance the fluid's thermal properties. In this work, density functional theory (DFT) is used to screen Diels–Alder reactions for use in aqueous thermal fluids. From an initial set of 52 reactions, four are identified with moderate aqueous solubility and predicted turning temperature near the liquid region of water. These reactions are selectively modified through 60 total functional group substitutions to produce novel reactions with improved solubility and thermal properties. Among the reactions generated by functional group substitution, seven have promising predicted thermal properties, significantly improving specific heat (by as much as 30.5%) and energy storage density (by as much as 4.9%) compared to pure water. 相似文献
997.
预测材料异质结的界面原子结构对于理解界面对性能的影响至关重要. 目前, 从理论上预测材料界面结构仍具有极大挑战, 主要是缺乏普适有效的理论计算方法. 本文介绍了本课题组在异质结界面结构预测方面取得的最新进展. 结合马氏体相变唯象理论、 图论和随机表面行走算法, 提出了界面结构的一种有效预测方法, 可以实现自动化的计算预测. 通过GaP/TiO2半导体异质结等展示了该方法的有效性和在催化等领域的应用前景. 相似文献
998.
Yaosong Huang Yugong Chen Mingfei Zhou 《International journal of quantum chemistry》2020,120(24):e26415
Hexamethyldisiloxane [HMDSO, (CH3)3-SiOSi-(CH3)3] is an important precursor for SiO2 formation during flame-based silica material synthesis. As a result, HMDSO reactions in flame have been widely investigated experimentally, and many results have indicated that HMDSO decomposition reactions occur very early in this process. In this paper, quantum chemical calculations are performed to identify the initial decomposition of HMDSO and its subsequent reactions using the density functional theory at the level of B3LYP/6-311+G (d, p). Four reaction pathways—(a) Si O bond dissociation of HMDSO, (b) Si C bond dissociation of HMDSO, (c) dissociation and recombination of Si O and Si C bonds, and (d) elimination of a methane molecule from HMDSO—have been examined and identified. From the results, it is found that the barrier of 84.38 kcal/mol and Si O bond dissociation energy of 21.55 kcal/mol are required for the initial decomposition reaction of HMDSO in the first pathway, but the highest free energy barrier (100.69 kcal/mol) is found in the third reaction pathway. By comparing the free energy barriers and reaction rate constants, it is concluded that the most possible initial decomposition reaction of HMDSO is to eliminate the CH3 radical by Si C bond dissociation. 相似文献
999.
Malak Azmat Ali G. Murtaza Afzal Khan Eman Algrafy Asif Mahmood Shahid M. Ramay 《International journal of quantum chemistry》2020,120(19):e26357
Highly spin-polarized ferromagnetic materials are essential for efficient spintronic devices. Here, 100% spin-polarized compounds Rb2TaZ6 (Z = Cl, Br) studied via density functional theory are reported. These compounds show stability in the ferromagnetic phase with cubic symmetry and half metallic behavior, thereby exhibiting a nonzero direct band gap in the spin-down channel and zero band gap in the spin-up configuration. The Ta-d sates contribute mainly to the net magnetic moments as explained by the crystal field theory and density of states. High Curie temperatures of 960.35 and 1021.74 K for Ra2TaCl6 and Rb2TaBr6, along with maximum spin polarizability, make these compounds favorable for efficient spintronic applications. 相似文献
1000.