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151.
A general molecular mechanics (MM) model for treating aqueous Cu2+ and Zn2+ ions was developed based on valence bond (VB) theory and incorporated into the atomic multipole optimized energetics for biomolecular applications (AMOEBA) polarizable force field. Parameters were obtained by fitting MM energies to that computed by ab initio methods for gas‐phase tetra‐ and hexa‐aqua metal complexes. Molecular dynamics (MD) simulations using the proposed AMOEBA‐VB model were performed for each transition metal ion in aqueous solution, and solvent coordination was evaluated. Results show that the AMOEBA‐VB model generates the correct square‐planar geometry for gas‐phase tetra‐aqua Cu2+ complex and improves the accuracy of MM model energetics for a number of ligation geometries when compared to quantum mechanical (QM) computations. On the other hand, both AMOEBA and AMOEBA‐VB generate results for Zn2+–water complexes in good agreement with QM calculations. Analyses of the MD trajectories revealed a six‐coordination first solvation shell for both Cu2+ and Zn2+ ions in aqueous solution, with ligation geometries falling in the range reported by previous studies. © 2012 Wiley Periodicals, Inc. 相似文献
152.
Michael Dolg 《Theoretical chemistry accounts》2005,114(4-5):297-304
Energy-consistent relativistic pseudopotentials for 3d-transition metals Sc to Ni based on modified valence energies are proposed. The pseudopotentials are adjusted at the finite
difference level within the intermediate coupling scheme with respect to multi-configuration Dirac–Hartree–Fock data based
on the Dirac–Coulomb Hamiltonian with an estimate of the Breit contributions in quasidegenerate perturbation theory. Typically
a few hundred to thousand J levels arising from about 35 to 40 configurations ranging from the anion down to the highly charged
cation are considered as references. It is shown that introducing a small common energetic shift of all valence energies reduces
the errors in the parameter adjustment considerably. Results of highly correlated atomic and molecular test calculations using
large basis sets and basis set extrapolation techniques are presented.
To be submitted to Theoretical Chemistry Accounts (special volume on the occasion of Prof. Dr. H. Stoll's 60th birthday) 相似文献
153.
由于全球的工农业的迅速发展,水污染已成为人类所面临的最大危机。基于半导体光催化法是治理水污染的绿色技术之一,能够有效地降解和去除水中的污染物。在众多光催化材料中,金属氧化物半导体由于其具有低毒性、高稳定性和对水溶液中化学腐蚀的较高的抵抗力等优点,而被科学家们广泛地研究和应用。其中,三元组分的金属氧化物因其具有较窄的禁带宽度和可见光响应性质,在光催化降解领域上的能力已经超过其他的金属化合物。本文系统地介绍了两种典型的三元金属氧化物——钨酸铋和钼酸铋,围绕着基于钨酸铋和钼酸铋的复合型催化剂的制备和在光催化降解废水处理领域中的应用以及发展进行了综述,提出了目前关于钨酸铋和钼酸铋的复合材料的设计、机理研究和改性修饰方法中的所存在的主要问题,并对未来的发展趋势进行了展望。 相似文献
154.
Xiaoling Yang Jiayun Li Yu Liu Jiajian Peng Tianbo Li 《Phosphorus, sulfur, and silicon and the related elements》2019,194(1-2):83-86
The catalytic activities of titanium alkoxides and alkali metal alkoxides for hydrosilylation of unfunctionalized olefins have been studied. Titanium(IV) alkoxides showed excellent catalytic activity, while alkali metal alkoxides have low catalytic activity for the hydrosilylation of olefins. However, by using titanocene dichloride as an additive, alkali metal alkoxides showed also excellent catalytic property for hydrosilylation. In comparison with titanium alkoxides, no α-adduct was obtained by using alkali metal alkoxides/Cp2TiCl2 as catalysts. 相似文献
155.
Elena Kolodzeiski Dr. Saeed Amirjalayer 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(6):1263-1268
Photoresponsive functional materials have gained increasing attention due to their externally tunable properties. Molecular switches embedded in these materials enable the control of phenomena at the atomic level by light. Metal–organic frameworks (MOFs) provide a versatile platform to immobilize these photoresponsive units within defined molecular environments to optimize the intended functionality. For the application of these photoresponsive MOFs (pho-MOFs), it is crucial to understand the influence of the switching state on the host–guest interaction. Therefore, we present a detailed insight into the impact of molecular switching on the intermolecular interactions. By performing atomistic simulations, we revealed that due to different interactions of the guest molecules with the two isomeric states of an azobenzene-functionalized MOF, both the adsorption sites and the orientation of the molecules within the pores are modulated. By shedding light on the host–guest interaction, our study highlights the unique potential of pho-MOFs to tailor molecular interaction by light. 相似文献
156.
Qiang Liu Hubert Meissel Ilia Sadykov Simon Jones Nick Van Dijk Przemyslaw Rzepka Luca Artiglia Marco Ranocchiari Jeroen A. van Bokhoven 《Helvetica chimica acta》2021,104(7):e2100082
Stability studies on supported metal nanoparticles are essential for gaining insight into the design and optimization of high-performance materials. In this work, the dissolutions of Pt-based catalysts in HBr/Br2 mixture of various concentration regimes were studied and correlated with material structural properties. The dissolution of metal nanoparticles was enhanced by adding Br2 to the HBr solution. Comparing with commercial Pt/C catalyst, the well-alloyed PtIr/C catalyst was observed to exhibit high resistance towards dissolution. In addition, regulating the accessibility of the metal sites to dissolution-inducing species contributed to the marked stability of the nanoparticles in HBr/Br2 solutions, as shown for the surface-modified PtIr/C catalysts with organic diamine molecules. 相似文献
157.
Adsorption of Pb2+ ions on the combustion derived nanosized γ-Fe2O3 and its thiourea complex composite is reported. The adsorbents upon adsorption of Pb2+ ions are characterised by X-ray diffraction, scanning electron microscopy, energy dispersive X-ray microanalysis and infrared spectroscopy techniques. The eluent is characterised by atomic absorption spectroscopy for the estimation of Pb2+ ions. The reduction in the amount of lead after adsorption was estimated to be around 50% in case of complex composite adsorbent and around 15% in case of the γ-Fe2O3 adsorbents. Orthorhombic PbSO4 precipitated out from the eluent and is reported with a model reaction. Adsorption of lead onto the complex composite is explained through the formation of a surface tertiary complex. The advantage of employing a thiourea-γ-Fe2O3 complex composite as solid adsorbent for the adsorption of heavy metal pollutants is envisaged in the present investigation. 相似文献
158.
Pasynskii A. A. Grigoriev V. N. Torubaev Yu. V. Blokhin A. I. Shapovalov S. S. Dobrokhotova Zh. V. Novotortsev V. M. 《Russian Chemical Bulletin》2003,52(12):2689-2700
Transmetallation of the dichalcogenide complexes [CpMn(CO)2]2(-X2) (X = S or Se) with M(CO)5(thf) (M = Cr or W) afforded new heterometallic complexes CpMn(CO)2(-Se2)Cr(CO)5, CpMn(CO)2(-Se2)[Cr(CO)5]2, CpMn(CO)2(-X2)[W(CO)5]2 (X = S or Se), and CpMn(CO)2(-Se2)[Cr(CO)5][W(CO)5]. According to the X-ray diffraction data, their molecular structures contain the cyclic MnX2 fragments coordinated by one or two M(CO)5 groups via the X atoms. Study of thermal decomposition of the manganese complexes with different Mn : M : X ratios (M = Cr, W; X = S, Se, Te) by differential scanning calorimetry (DSC) and thermogravimetry demonstrated that this process took place at rather low temperatures (100—400 °C) and was accompanied by complete elimination of the CO groups followed by elimination of the Cp groups. At any metal to chalcogen ratio, the resulting inorganic chalcogenides contained no impurities of metal oxides and carbides. 相似文献
159.
F. A. Selimov O. A. Ptashko A. A. Fatykhov N. R. Khalikova U. M. Dzhemilev 《Russian Chemical Bulletin》1993,42(5):872-878
The linear and cyclic cooligomerization of 2-vinyl-, 2-methyl-5-vinyl-, and 4-vinylpyridines with 1,3-dienes and trienes catalyzed by complexes of transition metals (Fe, Co, Ni, Mn, Cr, Pd, Ru, Rh, and Zr) was carried out to give unsaturated pyridines containing alkenyl and cycloalkenyl substituents.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 916–921, May, 1993. 相似文献
160.
StudiesonColloidalPropertiesofMixedMetalHydroxide-ClayAqueousSuspensionNOUwan-guo;ZHANGChun-guang;SUNDe-jun;HANShu-huaandWANG... 相似文献