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971.
We present an integrated computational tool, rooted in density functional theory, the polarizable continuum model, and classical molecular dynamics employing spherical boundary conditions, to study the spectroscopic observables of molecules in solution. As a test case, a modified OPLS-AA force field has been developed and used to compute the UV and NMR spectra of acetone in aqueous solution. The results show that provided the classical force fields are carefully reparameterized and validated, the proposed approach is robust and effective, and can also be used by nonspecialists to provide a general and powerful complement to experimental techniques. 相似文献
972.
V. E. Schneider E. E. Tornau A. A. Vlasova A. A. Gurskas 《Journal of inclusion phenomena and macrocyclic chemistry》1985,3(3):235-242
Clathrate thermodynamic stability conditions and the phase transitions associated with either the orientational ordering of the guest molecules or with the condensation of the guest molecules in the host lattice are investigated by means of the common microscopic model. The theory proposed describes the thermodynamic properties of -hydroquinone (Q
) clathrates. The dielectric constant (T) was measured experimentally inQ
·CH3OH andQ
·SO2 in the temperature range from 4.2 to 300 K and the phase transitions were found. It is shown that the theory qualitatively explains the experimental data obtained.Dedicated to Professor H. M. Powell. 相似文献
973.
A new effective approach to the synthesis of a small library of 2-amino-5-arylidene-1,3-thiazol-4(5H)-ones was reported using solvent-free reaction conditions under microwave irradiation. In the first step, rhodanines were subjected to Knoevenagel condensation with aryl aldimines according to a facile one-pot protocol. Then the (5Z)-5-arylidene rhodanine derivatives were transformed directly into the corresponding 2-amino-1,3-thiazol-4(5H)-ones by sulfur/nitrogen displacement reaction under microwaves with retention of configuration and good overall yields. 相似文献
974.
锂离子电池负极合金CoSn和Cu-Sn的制备与表征 总被引:9,自引:0,他引:9
CoSn alloy and Cu-Sn samples were synthesized by H2-reduction following solid-state reaction between Co(Ⅱ), Cu(Ⅱ), Sn(Ⅳ) and NaOH at ambient temperature. The samples were characterized by XRD, SEM. The results showed that CoSn alloy (80~200nm) is globe-shaped, ultrafine hexagonal material, and Cu-Sn alloy powder consists of two phases, i.e. Cu6Sn5 and Cu3Sn. Cu-Sn powder has spherical morphology and the particle size is estimated to be 60~70nm. The electrochemical performances of CoSn alloy and Cu-Sn powder were studied using lithium-ions model cell Li/LiPF6 (EC+DMC)/CoSn (or Cu-Sn). It was demonstrated the reversible discharge capacities for 10 cycles keep above 280mAh·g-1 for nanophase Cu-Sn, and 60mAh·g-1 for CoSn alloy. Differ-ential capacity plots showed that the reaction mechanisms of Cu-Sn with lithium were reversible. 相似文献
975.
In Situ IR Spectroscopic Studies on Molybdenum Nitride Catalysts: Active Sites and Surface Reactions
Recent IR spectroscopic studies on the surface properties of fresh Mo2N/-Al2O3 catalyst are presented in this paper. The surface sites of fresh Mo2N/-Al2O3, both Mo+ (0<<2) and N sites, are probed by CO adsorption. Two characteristic IR bands were observed at 2045 and 2200 cm-1, due to linearly adsorbed CO on Mo and N sites, respectively. The surface N sites are highly reactive and can react with adsorbed CO to form NCO species. Unlike adsorbed CO on reduced passivated one, the adsorbed CO on fresh Mo2N/-Al2O3 behaves similarly to that of group VIII metals, suggesting that fresh nitride resembles noble metals. It is found that the surface of Mo nitrides slowly transformed into sulfide under hydrotreating conditions, which could be the main reason for the activity drop of molybdenum nitride catalysts in the presence of sulfur-containing species. Some surface reactions, such as selective hydrogenation of 1,3-butadiene, isomerization of 1-butene, and hydrodesulfurization of thiophene, were studied on both fresh and reduced passivated Mo2N/-Al2O3 catalysts using IR spectroscopy. The mechanisms of these reactions are proposed. The adsorption and reaction behaviors of these molecules on fresh molybdenum nitride also resemble those on noble metals, manifesting the unique properties of fresh molybdenum nitride catalysts. Mo and N sites are found to play different roles in the adsorption and catalytic reactions on the fresh Mo2N/-Al2O3 catalyst. Generally, Mo sites are the main active sites for the adsorption and reactions of adsorbates; N sites are not directly involved in catalytic reactions but they modify the electronic properties of Mo sites. 相似文献
976.
Ulrich Jordis 《Monatshefte für Chemie / Chemical Monthly》1988,119(10):1179-1184
Carbophilic reaction of 1,3-benzodithiole-2-thione (1) with trideuteroborane · dimethylsulfide, synthesized from NaBD4 and BF3 ·Me
2S inTHF, gave 2,2-dideutero-1,3-benzodithiole (5 b) as well as the minor side-products7 b,8 and9 b. 相似文献
977.
978.
A. Yamazaki Y. Inoue M. Koike T. Sakamoto R. Otsuka 《Journal of Thermal Analysis and Calorimetry》1993,40(1):85-97
Thomsonite with ideal chemical composition and with an ordered framework structure was synthesised hydrothermally from zeolite Na?A, which was ground to X-ray amorphous, with 0.05 mol dm?3 CaCl2 solution at 200°C. The dehydration behaviour of the prepared thomsonite was examined by TG-DTA. It was revealed that thomsonite lost most of zeolitic water below 450°C in three steps at about 180°, 340° and 390°C. The peak profiles of, the two higher-temperature endotherms were sharp and similar, and the weight loss at each step was approximately equal. 相似文献
979.
E. Miyoshi T. Iura Y. Sakai H. Tochihara S. Tanaka H. Mori 《Journal of Molecular Structure》2003,630(1-3):225-232
We investigated the interactions between the Si(111) surface and the Na, Mg, and Al atoms using cluster model calculations. Calculations were performed at levels of complete-active-space self-consistent-field (CASSCF) and multi-reference singly and doubly excited configuration interaction (MRSDCI) calculations using the model core potential method. Our calculations revealed that the most favorable sites of Na, Mg, and Al adsorption on Si(111) are on top (T1), bridge (B2), and 3-fold filled (T4) sites, respectively. The nature of chemical bonds between these metal atoms and the dangling bonds of the surface Si atoms are found to be essentially covalent. 相似文献
980.
Robert Martin Nicole Gros Volker Böhmer Hermann Kämmerer 《Monatshefte für Chemie / Chemical Monthly》1979,110(5):1057-1066
TheFries rearrangement of different methoxy benzoates has been investigated. Frompara-methoxy benzoates the corresponding hydroxy-4-methoxy benzophenones could be obtained in good yields by treatment withLewis acids (especially TiCl4) in nitromethane at 20°C (4-hydroxy derivatives) or without solvent at 120°C (2-hydroxy derivatives). Under the same conditions only demethylation occurs withortho-methoxy benzoates leading to the corresponding salicylates. Small amounts of hydroxy-2-methoxy benzophenones were obtained by treatment with polyphosphoric acid. 相似文献