The accuracy of the quantum/classical time-dependent self-consistent field treatment to reaction dynamics of large systems

A method is proposed to predict the accuracy of the quantum/classical time-dependent self-consistent field (Q/C TDSCF) treatment in the calculation of reaction probabilities. This method was derived based on comparisons of calculated reaction probabilities between the collinear and the three dimensional results for the benchmark O(3P) + HCl reaction, which shows that the accuracy of the Q/C TDSCF reaction probabilities does not change from the collinear to the three dimensional dynamics. In addition, an energy shift correction is introduced to improve the accuracy of the Q/C TDSCF results. The results from studies of the O(3P) + HCl reaction indicate that the inclusion of this simple shift in the Q/C TDSCF treatments allows us to obtain accurate reaction probabilities within the energy range of chemical and biological interest. Our analysis indicates that this shift is related to the symmetry of the potential energy surface between the reactant and product channels in the transition state region.