The validities of centrifugal sudden approximations in chemical reaction dynamics

Abstract

In this review article, we discuss and analyze the validities of centrifugal sudden (CS) approximations in chemical reactions, with emphasis on the recent progress in the comparison studies of close-coupling and CS approximations in chemical dynamics both adiabatically and nonadiabatically. All these relevant studies are performed using the time-dependent wave packet approach, focusing on several typical and benchmark chemical reactions, for example, the triatomic adiabatic ionmolecule reactions of Ne

Dynamics of the O + H2+ → OH+ + H, OH + H+ proton and hydrogen atom transfer reactions on the two lowest potential energy surfaces

“…For each initial condition (E col = 0.05-0.50 eV, v = 0, j = 0) batches of 1.0 Â 10 5 trajectories were calculated on both PESs The statistical error (one standard deviation) of the cross sections was less than 0.15% for all conditions studied, whereas in the case of the product state distributions the standard deviation was maintained below 2%. Additional QCT calculations were also Some calculations were also carried out (E col r 0.50 eV, v = 0, j = 0) by means of the time dependent real wave packet quantum method, 20 using the centrifugal sudden approximation, 21 which has been applied to a wide range of reactions 22 and is quite satisfactory for this 2 and related systems, 3,6 in order to compare the quantum and quasiclassical cross section results. Basically, the RWP-CS method propagates the real part of a wave packet under the action of an inverse cosine mapping of a shifted and scaled Hamiltonian operator, using the Chebyshev's iterations.…”

Studies of the Coriolis coupling effect on reaction dynamics of ${\rm{H}}({}^{2}{\rm{S}})+{\rm{O}}{{\rm{H}}}^{+} \rightarrow {\rm{O}}({}^{3}{\rm{P}})+{{\rm{H}}}_{2}^{+}({{\rm{{\rm X}}}}^{2}{{\rm{\Sigma }}}_{{\rm{g}}}^{+})$ using the time dependent wave packet method

“…Thus, in order to save the computational cost, the CSA calculation, which does not consider the CC effect, has been used to investigate the reactions dynamics. In recent years, theoretical researchers have an interest in the CC effect of chemical reaction [24][25][26][27][28][29][30][31][32][33][34][35][36][37][38][39][40][41][42][43]. The previous study shows that the CSA results were in good agreement with the CC ones for the direct over the barrier reaction mechanism [38,39].…”