One-carbon unit transfer reaction of imidazolinium with 1,2-diaminobenzene has been studied with semi-empirical molecular orbital calculations, PM3. The result shows that there are two ways to complete this reaction b...One-carbon unit transfer reaction of imidazolinium with 1,2-diaminobenzene has been studied with semi-empirical molecular orbital calculations, PM3. The result shows that there are two ways to complete this reaction because the imidazolinium ring has two different breaking patterns. These two ways both have seven steps, including two proton-migrating steps that limit the rate of the reaction. The structures and energies of the intermediates and transition states have been calculated.展开更多
A theoretical scheme is presented which is based on an activation model for calculating the rate of the electron- exchange reaction between transition metal complexes in aqueous solution and applies to electron transf...A theoretical scheme is presented which is based on an activation model for calculating the rate of the electron- exchange reaction between transition metal complexes in aqueous solution and applies to electron transfer system.The activation parameter and activation energy of the system are obtained via the activation model. The slopes of the potential energy surfaces (curves) of the reacting system at the separated reactants are calculated from the fitted potential energy curves. The coupling matrix element is determined by using the perturbation theory and numerical integral method. Theoretical rate constants are obtained for the system at both UHF/6- 311G and UMP2/6- 311G levels.The agreement of the theoretical results with experimetal values is excellent.This fact indicates the scheme proposed is feasible and accurate in studying the self- exchange eletron transfer reaction.展开更多
An extended LCAC\|SW(Linear Combination of Arrangement Channels\|Scattering Wavefunction) quantum scattering dynamic method combined with \%ab initio\% quantum chemical calculations has been used to study the formatio...An extended LCAC\|SW(Linear Combination of Arrangement Channels\|Scattering Wavefunction) quantum scattering dynamic method combined with \%ab initio\% quantum chemical calculations has been used to study the formation mechanism of the resonance states for ion\|pair formation reaction Na+I\-2 Na\+++I\+-\-2. Resonance energy and width or lifetime for the first resonance peak were calculated. Resonance can be identified to Feshbach resonance and the physical interpretation was given.展开更多
On the basis of ZINDO program, we have designed a program to calculate the nonlinear second order polarizabilities β ijk and β μ according to the SOS equation. The second order nonlinear optical properties of diaza...On the basis of ZINDO program, we have designed a program to calculate the nonlinear second order polarizabilities β ijk and β μ according to the SOS equation. The second order nonlinear optical properties of diazadistyrene derivatives were studied. The calculated results reveal that the introduction of pyrimidine does not influence the transparency but give a rise to large values of β. For the corresponding stilbene derivatives, the effect of the location of pyrimidine on the values of β is greater.展开更多
Reaction resonance or Feshbach resonance in polyatomic reaction is one of the most fascinating phenomena in chemical reaction dynamics. The HO+CH4→HO+CH3 reaction is one of the pivotal polyato-mic reactions concerned...Reaction resonance or Feshbach resonance in polyatomic reaction is one of the most fascinating phenomena in chemical reaction dynamics. The HO+CH4→HO+CH3 reaction is one of the pivotal polyato-mic reactions concerned with both the experimental and theoretical scientists. Reaction probabilities and other dynamic properties of this system were calculated with quantum scattering theory method, but a simple QH(v)+HO(j)→Q+H2O(m,n) reaction model was used, in which only three degrees of freedom and the rotating of OH were considered while making CH3 as a pseudo atom. In this paper, by an ab initio method, partial potential energy surface(PPES) was constructed and all the 15 internal degrees-freedom were given. Feshbach resonance mechanism of this reaction can be obtained by the dynamic Eyring Lake on the PPES and the lifetime of the reactive resonance-state can be estimated using the gap of the vibrational energy levels of transient collision complex in the critical transition-state region. Above interesting dynamic properties would not be given by simple pseudo atomic reaction model.展开更多
The relationship between activity coefficient and molecule exchanging energy of surfactants in the surface monolayer of binary surfactant aqueous solutions has been deduced with the help of two dimensional crystal mod...The relationship between activity coefficient and molecule exchanging energy of surfactants in the surface monolayer of binary surfactant aqueous solutions has been deduced with the help of two dimensional crystal model. The results show the relationship between the synergism of surfactants and the molecule exchanging energy. Through the parameter of molecule interaction( β s), the value of the molecule exchanging energy can be obtained by equation ε =2.3×10 -24 β s T that has been examined with six typical surfactant systems.展开更多
文摘One-carbon unit transfer reaction of imidazolinium with 1,2-diaminobenzene has been studied with semi-empirical molecular orbital calculations, PM3. The result shows that there are two ways to complete this reaction because the imidazolinium ring has two different breaking patterns. These two ways both have seven steps, including two proton-migrating steps that limit the rate of the reaction. The structures and energies of the intermediates and transition states have been calculated.
文摘A theoretical scheme is presented which is based on an activation model for calculating the rate of the electron- exchange reaction between transition metal complexes in aqueous solution and applies to electron transfer system.The activation parameter and activation energy of the system are obtained via the activation model. The slopes of the potential energy surfaces (curves) of the reacting system at the separated reactants are calculated from the fitted potential energy curves. The coupling matrix element is determined by using the perturbation theory and numerical integral method. Theoretical rate constants are obtained for the system at both UHF/6- 311G and UMP2/6- 311G levels.The agreement of the theoretical results with experimetal values is excellent.This fact indicates the scheme proposed is feasible and accurate in studying the self- exchange eletron transfer reaction.
文摘An extended LCAC\|SW(Linear Combination of Arrangement Channels\|Scattering Wavefunction) quantum scattering dynamic method combined with \%ab initio\% quantum chemical calculations has been used to study the formation mechanism of the resonance states for ion\|pair formation reaction Na+I\-2 Na\+++I\+-\-2. Resonance energy and width or lifetime for the first resonance peak were calculated. Resonance can be identified to Feshbach resonance and the physical interpretation was given.
文摘On the basis of ZINDO program, we have designed a program to calculate the nonlinear second order polarizabilities β ijk and β μ according to the SOS equation. The second order nonlinear optical properties of diazadistyrene derivatives were studied. The calculated results reveal that the introduction of pyrimidine does not influence the transparency but give a rise to large values of β. For the corresponding stilbene derivatives, the effect of the location of pyrimidine on the values of β is greater.
文摘Reaction resonance or Feshbach resonance in polyatomic reaction is one of the most fascinating phenomena in chemical reaction dynamics. The HO+CH4→HO+CH3 reaction is one of the pivotal polyato-mic reactions concerned with both the experimental and theoretical scientists. Reaction probabilities and other dynamic properties of this system were calculated with quantum scattering theory method, but a simple QH(v)+HO(j)→Q+H2O(m,n) reaction model was used, in which only three degrees of freedom and the rotating of OH were considered while making CH3 as a pseudo atom. In this paper, by an ab initio method, partial potential energy surface(PPES) was constructed and all the 15 internal degrees-freedom were given. Feshbach resonance mechanism of this reaction can be obtained by the dynamic Eyring Lake on the PPES and the lifetime of the reactive resonance-state can be estimated using the gap of the vibrational energy levels of transient collision complex in the critical transition-state region. Above interesting dynamic properties would not be given by simple pseudo atomic reaction model.
文摘The relationship between activity coefficient and molecule exchanging energy of surfactants in the surface monolayer of binary surfactant aqueous solutions has been deduced with the help of two dimensional crystal model. The results show the relationship between the synergism of surfactants and the molecule exchanging energy. Through the parameter of molecule interaction( β s), the value of the molecule exchanging energy can be obtained by equation ε =2.3×10 -24 β s T that has been examined with six typical surfactant systems.
