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991.
A cumulative selection procedure for choosing configuration functions for inclusion in CI calculations is described. The objective of the method is to obtain equal energy loss, relative to unselected calculations, for different states and different regions of the potential surface. Results obtained from calculations on the BH molecule indicate an overall advantage in comparison to the threshold selection procedure, particularly with regard to molecular geometry changes. 相似文献
992.
Langlet J. Claverie P. Pullman B. Piazzola D. Daudey J. P. 《Theoretical chemistry accounts》1977,46(2):105-116
The effect of water on the conformational preferences of acetylcholine has been studied within the discrete, the continuum and the combined discrete-continuum models described in parts I and II of this series. All the models lead to the conclusion that the trans-gauche form which is, following refined quantum-mechanical computations, the intrinsically preferred one and the one observed in the crystal of acetylcholine and of a number of analogues should remain also the preferred conformation in water. This result agrees with NMR studies. The results of the empirical discrete model used here compare favorably to those obtained by an ab initio super-molecule treatment. The continuum model utilized here represents a net improvement above such models utilized in other works. 相似文献
993.
A non-empirical molecular orbital method, particularly suitable for calculations on cage-like molecules, is described. The method uses as basis functions the set of free-electron functions which are the solutions of Schrödinger's equation for an electron confined between two concentric, spherical potential energy barriers. Application of the theory to the SCF calculation of the energies of the delocalized electrons in benzene and tetrasulphur tetranitride shows that the model is capable of interpreting the properties of such systems. However, it does highlight a difficulty in the calculation of excited state energies with one-centre models which appears to be largely unrecognized.Extension of the method to a consideration of all the valence electrons, using P4 as an example, reveals problems the origin of which is an inadequate treatment of the core electrons. It is suggested that these problems may best be dealt with by use of a suitable pseudo potential. 相似文献
994.
Aromatic peptide nucleic acid analogs having an N-(2-aminobenzyl)glycine backbone (APNA 1) were previously identified as promising new leads for the design of polyaromatic DNA mimics. Structural modifications of 1, which lock the aromatic backbone into a unique conformation, while maintaining the same space distribution between the nucleobases as in 1, were investigated. The electrostatic potential of the aromatic backbone was also modified in an attempt to improve the solubility of these compounds in aqueous media and to evaluate how the quadrapole of the aromatic backbone may influence the biophysical properties of the APNA oligomers. PNA hexamers containing a single monomer insert of each new APNA monomer were used to explore the hybridization properties of these analogs with poly rA and poly dA. Preliminary results indicated that these modifications do not seriously alter the molecular recognition properties of APNAs towards DNA and RNA. 相似文献
995.
Tetramethyldisilane-1,2-diyl bridged Dicyclopentadienyl and Diindenyl Metal Dichlorides of the Group 4 Metals – Crystal Structure of Dicyclopentadienyl and diindenyl metal dichlorides of the type Cp′? SiMe2SiMe2? Cp′MCl2 (Cp′ = C5H4, M = Ti ( 1 ), Zr ( 2 ), Hf ( 3 ); Cp′ = C9H7, M = Zr ( 4 ), Hf ( 5 )) were synthesized and characterized by means of their 1H, 13C, 29Si-n.m.r., MS, and IR spectra. The crystal structure of 2 was determined. 相似文献
996.
La2O3对Ni/γ-Al2O3甲烷化催化剂的助催化作用 总被引:14,自引:0,他引:14
我国将稀土作为助剂引入镍基甲烷化催化剂,大大提高了催化剂的活性和热稳定性,并已投入工业应用[1-3].稀土对不同镍催化剂反应性能及其作用机理的研究已有一些报导[3-7].谢有畅等观察到镍负载在经单层La2O3改性的γ-Al2O3表面,其晶粒要比没有La2O3时小得多.Rotgerink等认为添加La后反应速率的增加不只是由于几何效应,而是La对甲烷化本身有促进作用,单位镍表面的活性是随La含量不同而改变的,活性增加的同时表观活化能也增加[5].作为助剂的La2O3在氢还原和反应过程中的变化及其作用的研究和讨论较少,目前一般认为添… 相似文献
997.
998.
999.
Simultaneous determination of cobalt,copper, iron and vanadium in crude petroleum oils by HPLC 总被引:1,自引:0,他引:1
Summary A method has been developed for the simultaneous formation and solvent extraction of cobalt (II), copper (II), iron (II) and vanadium (IV) complexes of bis (acetylpivalylmethane)ethylenediamine (H2APM2en) in methyl isobutyl ketone. The complexes are eluted from a reversed phase HPLC column with a mixture of methanol:water:acetonitrile and detection was at 260 nm. The method has been applied to the simultaneous determination of cobalt, copper, iron and vanadium in crude petroleum oils at the ng level. 相似文献
1000.
Jian X. Gao Jian C. Wang Chong L. Song T. Liu Tian D. Hu Ya N. Xie J. Zhang G. Wang H. Yang 《Journal of solution chemistry》2006,35(1):113-119
NMR spectroscopy was used to show that the symmetry of the crown ether bis(C6) is increased by an increase of the alkali metal
cation radius. The EXAFS spectrum demonstrates that a seven oxygen atom coordinated configuration is present in the bis(C6)/Cs+/NPME system, where NPME denotes o-nitrophenylmethyl ether. The seventh oxygen in this complex, besides the six crown ether oxygens of bis(C6), may come either
from a H2O molecule or an NO3− ion. 相似文献