Matrix element of the Gallilean invariant nonrelativistic reduction of the pseudoscalar-pseudovector interaction has been
calculated for free pion absorption by a single nucleon inside the nucleus of16O. The Hartree-Fock wavefunctions obtained with the unitary-model-operator approach starting with the hard-core nucleon-nucleon
interaction have been used for the π-capturing nucleon in the initial state. The initial pion distortion in the presence of
nuclear field of the absorbing nucleus prior to its absorption together with the Coulomb interaction with the finite nuclear
size has been taken into account. The distortion of the emitted proton in the field of the residual nucleus has also been
considered. The differential cross-sections have been obtained and calculated results are compared with the previous experimental
and theoretical work. 相似文献
In general, sensitization of lanthanide(III ) ions by organic sensitizers is regarded to take place via the triplet state of the sensitizers. Herein, we show that in dansyl‐ and lissamine‐functionalized Nd3+complexes energy transfer occurs from the singlet state of the sensitizers to the Nd3+center. No sensitized emission was observed in the corresponding complexes with Er3+, Yb3+, and Gd3+ions. Furthermore, the fluorescence of the sensitizers was quenched only in the Nd3+complex and not in the complexes with the other ions. Only Nd3+centers can accept energy from the singlet state of the dyes, because the excited states of Nd3+have a high spectral overlap with the fluorescence of the dansyl and lissamine sensitizers, and because the selection rules allow a fast energy transfer, which apparently is competitive with the fluorescence.相似文献
A comparative study of absorption and fluorescence maxima of 4,4′-diaminodiphenyl sulphone (4DADPS), 3,3′-diaminodiphenyl sulphone (3DADPS) and 2-aminodiphenyl sulphone (2ADPS) in different solvents reveals that (i) solvatochromic shifts are found to be mainly due to interaction of solvents with amino group, (ii) in any one solvent the net solvatochromic shifts of two amino groups are less than that of one amino group, (iii) fluorescence shift from cyclohexane to water is a maximum for 4DADPS and a minimum for 2ADPS and (iv) 4DADPS and 3DADPS possess more twisted intramolecular charge transfer character than 2ADPS. The excited-state acidity constants, determined by fluorimetric titration and Förster cycle methods, have been reported and discussed. 相似文献
The diphosphate ester (ThDP) of thiamin (vitamin B1) is an important cofactor of enzymes within the carbohydrate metabolism. The initial reaction step shared by all ThDP-dependent enzymes is the deprotonation of the C2–H of the thiazolium ring. The replacement of the 4′-amino group by a hydroxyl one in the pyrimidine ring leads to the oxy-ThDP analogue which is known as an antagonist in thiamin catalysis.
Ab initio and DFT calculations on the MP2/6-31G* and B3LYP/6-31G* level were performed to study the proton relay function in thiamin and oxythiamin systems. Both MP2 and B3LYP calculations show significant differences of the reaction coordinate of the ylide formation in the systems. Tautomers, protonated and deprotonated species of both systems show different trends regarding their stability. The influence of correlation effects on the results is discussed by comparison with the HF-SCF/6-31G* data. Frequency calculations on the B3LYP/6-31G* level were performed to characterize the minima and transition state structures, respectively. 相似文献
Hydrogen abstraction reaction, H C2H4 --H2 C2H2 was studied by using A initio SCF method. Ge-ometries were fully optimized at SCF level and energies were computed at STO-3G basis set for reactants and transition state. Vibrational analysis was performed thereupon. Finally, the rate constant calculations were carried out at different temperatures for all range of reaction temperature according to Eyring's sbwlute reaction rate theory. The calculated activation energy is 12. 68 kcal/mol, lower than observed value (H. S kcal/mol) by 1. 82 kcal/mol only. The agreement of the calculated rate constants with the experiments is satisfactory. 相似文献
The modeling of liquid–vapor equilibrium in ternary mixtures that include substances found in alcoholic distillation processes of wine and musts is analyzed. In particular, vapor–liquid equilibrium in ternary mixtures containing water + ethanol + cogener has been modeled using parameters obtained from binary mixture data only. The congeners are substances that although present in very low concentrations, of the order of part per million, 10−6 to 10−4 mg/L, are important enological parameters [1] and [2]. In this work two predictive models, the PSRK equation of state and the UNIFAC liquid phase model and two semipredictive activity coefficient models: NRTL and UNIQUAC have been used. The results given by these different models have been compared with literature data and conclusions about the accuracy of the models studied are drawn, recommending the best models for correlating and predicting the phase equilibrium in this type of mixtures. 相似文献
In this work, the authors use complete active space self-consistent field method to investigate the photoinduced charge-separated states and the electron transfer transition in complexes ethylene-tetracyanoethylene and tetramethylethylene-tetracyanoethylene. Geometries of isolated tetracyanoethylene, ethylene, and tetramethylethylene have been optimized. The ground state and the low-lying excited states of ethylene and tetracyanoethylene have been optimized. The state energies in the gas phase have been obtained and compared with the experimentally observed values. The torsion barrier of tetracyanoethylene has been investigated through the state energy calculation at different conformations. Attention has been particularly paid to the charge-separated states and the electron transfer transition of complexes. The stacked conformations of the donor-acceptor complexes have been chosen for the optimization of the ground and low-lying excited states. Equilibrium solvation has been considered by means of conductor-like screening model both in water and in dichloromethane. It has been found that the donor and tetracyanoethylene remain neutral in complexes in ground state (1)A(1) and in lowest triplet state (3)B(1), but charge separation appears in excited singlet state (1)B(1). Through the correction of nonequilibrium solvation energy based on the spherical cavity approximation, pi-->pi* electron transfer transition energies have been obtained. Compared with the experimental measurements in dichloromethane, the theoretical results in the same solvent are found higher by about 0.5 eV. 相似文献
Summary. The evaluation of mutual solubility data for systems water with n-alkanes, isoalkanes, and cycloalkanes along the three phase line is reported and a formula for the prediction of solubility
of alkanes in water is developed. Then a cubic equation of state with an added term, which accounts for hydrogen bonding is
used for correlation of liquid–liquid equilibrium data and for prediction of solubility of water in hydrocarbons using alkane
in water solubility data. Comparison of the predicted and experimental solubilities is performed using all accessible experimental
data. With this approach it is possible to predict the solubilities of water in alkanes with good accuracy over the temperature
range up to about 20 K below critical temperature. Solubility of alkanes in water can also be calculated using experimental
data for solubility of water in alkanes but results of these calculations are more sensitive to experimental errors of the
data.
Corresponding author: E-mail: macz@ichf.edu.pl
Received August 5, 2002; accepted (revised) September 13, 2002
Published online March 13, 2003
RID="a"
ID="a" Dedicated to Prof. Dr. H. Gamsj?ger on the occasion of his 70th birthday anniversary 相似文献