The properties of nonadiabatic trapping models of the reaction NH+H -N+H, are investigated in a collinear model as \veil as a non-collinear thermal reaction on the basis of theintrinsic reaction coordinate (IRC) intbr...The properties of nonadiabatic trapping models of the reaction NH+H -N+H, are investigated in a collinear model as \veil as a non-collinear thermal reaction on the basis of theintrinsic reaction coordinate (IRC) intbrmation obtained by ah initio calculations at QCISD/631 IG** ie\el. Using the unitied statistical theory fornonadiabatic trapping models. the thermal rateconstants over the temperature range of 2000-3000K are computed which are in excellent agreementwith the experiment results.展开更多
A new approach was employed to calculate the canonical (thermal) rate constant basedon unified statistical theory. All information for the calculation was obtained from ab initio meth-ods. The flux integral for any po...A new approach was employed to calculate the canonical (thermal) rate constant basedon unified statistical theory. All information for the calculation was obtained from ab initio meth-ods. The flux integral for any point of reaction coordinate was calculated by counting the numberof quantum states and applied to determine the dividing surfaces along the intrinsic reaction coor-dinate (IRC). The classical exchange reaction H2+H, as an example, was investigated. The IRC forthe reaction has been traced and detailed information of IRC was carried out at the QCISD/6-311 G** level .The calculated rate constants are well consistent with the experimental results.展开更多
The pathway of dehydrogenation reaction of silanol SiH3OH is investigated by ab initio Mo calculations using RHF/-31G basis set. The geometries of reactant, transition states and products are optimized on the singlet ...The pathway of dehydrogenation reaction of silanol SiH3OH is investigated by ab initio Mo calculations using RHF/-31G basis set. The geometries of reactant, transition states and products are optimized on the singlet potential energy surface of the ground state. The activation energies, reaction heats, statistical A factor and activation entropies are calculated. The vibrational analysis of the reactant and the transition states is made. The reaction crgodography along the intrinsic reaction coordinate (IRC) are performed to examine the reaction mechanism.展开更多
文摘The properties of nonadiabatic trapping models of the reaction NH+H -N+H, are investigated in a collinear model as \veil as a non-collinear thermal reaction on the basis of theintrinsic reaction coordinate (IRC) intbrmation obtained by ah initio calculations at QCISD/631 IG** ie\el. Using the unitied statistical theory fornonadiabatic trapping models. the thermal rateconstants over the temperature range of 2000-3000K are computed which are in excellent agreementwith the experiment results.
文摘A new approach was employed to calculate the canonical (thermal) rate constant basedon unified statistical theory. All information for the calculation was obtained from ab initio meth-ods. The flux integral for any point of reaction coordinate was calculated by counting the numberof quantum states and applied to determine the dividing surfaces along the intrinsic reaction coor-dinate (IRC). The classical exchange reaction H2+H, as an example, was investigated. The IRC forthe reaction has been traced and detailed information of IRC was carried out at the QCISD/6-311 G** level .The calculated rate constants are well consistent with the experimental results.
文摘The pathway of dehydrogenation reaction of silanol SiH3OH is investigated by ab initio Mo calculations using RHF/-31G basis set. The geometries of reactant, transition states and products are optimized on the singlet potential energy surface of the ground state. The activation energies, reaction heats, statistical A factor and activation entropies are calculated. The vibrational analysis of the reactant and the transition states is made. The reaction crgodography along the intrinsic reaction coordinate (IRC) are performed to examine the reaction mechanism.
