Solvent shift in water of π → π* transitions of the carbonyl group is evaluated making use of a recently proposed computdtional procedure for the continuum solvent model. Comparisons with the discrete model and with composite discrete-continuum procedures are performed. 相似文献
It is shown by proton NMR and quantum chemical PCILO calculations that monothio-β-ketones in solution exist as different isomers depending on substituents, solvent and temperature. In solvents with low dielectric constants the hydrogen-bridged cis enol form predominates, and is in fast equilibrium (in the NMR scale) with nonchelated trans enol forms down to ?100°C at least. Transition enthalpies are of the order of 7–15 kJ mol?1. In compounds with R2 = Me the rotation of the Me -CS group around the neighbouring C-C- bond can be detected and the thermodynamic and kinetic parameters estimated. The reason for the slowing down of this rotation, inferred from the line broadening in NMR, is probably the stabilization of a trans isomer by interaction between the protons of the methyl group and the lone pairs of the oxygen atom. There are no indications for the presence of chelated and non-chelated enethiol isomers from the PMR studies and quantum chemical calculations performed. 相似文献
As is known, if is a -Brownian motion, a process of form , , is a non-increasing -martingale. In this paper, we shall show that a non-increasing -martingale cannot be form of or , , which implies that the decomposition for generalized -Itô processes is unique: For arbitrary , and non-increasing -martingales , if then we have , and. As an application, we give a characterization to the -Sobolev spaces introduced in Peng and Song (2015). 相似文献