Time-dependent quantum wave packet dynamics of the C + OH reaction on the excited electronic state

Abstract

Quantum state-selected dynamics of C((3)P) + OH (X(2)Π) → CO(a(3)Π) + H ((2)S) reaction on its first excited electronic potential energy surface (1(2)A(")) is examined here using a time-dependent wave packet propagation approach. All partial wave contributions for the total angular momentum, J = 0-95, are included to obtain the converged cross sections and initial state-selected rate constants in the temperature range of 10-500 K. The reaction probability, as a function of collision energy, exhibits dense oscillatory structures owing to the formation of resonances during collision. These resonance structures also persist in reaction cross sections. The effect of reagent rotational and vibrational excitation on the dynamical attributes is examined and discussed. Reagent rotational excitation decreases the reactivity whereas, vibrational excitation of the reagent has minor effects on the reactivity. The results presented here are in good accord with those obtained using the time-independent quantum mechanical and quasi-classical trajectory methods.

Quantum Dynamical Study of the He + NeH+ Reaction on a New Analytical Potential Energy Surface

“…Rotational excitation disrupts the preferred geometry and inhibits reactivity, as is the case for j = 1 and 2. Similar results have been observed for He + H 2 + , 9,10 C + OH, 70 H + LiH, 71 and Li + HF 66 scattering systems with deep potential wells along the reaction paths. But further rotational excitation to a higher rotational state increases the reactant energy by a larger amount, and more product states become available.…”

Wave packet and statistical quantum calculations for the He + NeH+ → HeH+ + Ne reaction on the ground electronic state

“…6 The reaction cross sections for v 0 = 1, j 0 = 0 are very high at low collision energies and the magnitude decreases sharply with the increase in collision energy and remains almost constant with further increase in collision energy. Similar observations were reported for other barrierless exothermic processes 8,9,74 and for reactions with reactants in their vibrationally excited states in late barrier type surfaces. [5][6][7]81 In the present system, the barrier corresponds to the reaction endothermicity.…”

“…As is seen in Figure 1, vibrational excitation makes the reaction thermodynamically exothermic, which results in a strong enhancement in the reaction probabilities. For v 0 = 1, the reaction probabilities for lower J values start without any threshold, which is typical for barrierless exothermic reactions 2,3,8,9,74 and processes with reactants in vibrationally excited states. 5-7, 12, 25, 81 For J = 10, the SQM results are very small compared to the QM results in 0.0-0.1 eV energy range.…”

Electronic nonadiabatic effects in low temperature radical-radical reactions. I. C(3P) + OH(2Π)

“…First, there have been high-level SBO calculations for this system which, with the help of Eq. (1.1), led to low temperature rate constants [26][27][28][29][30][31] such as considered also in the present work. This allows us to compare the present results with this alternative treatment and to inspect the validity (or non-validity) of an approach based on Eq.…”