^{1}and Dmitri Babikov

^{1,a)}

### Abstract

The mixed quantum-classical theory developed earlier [M. Ivanov and D. Babikov, J. Chem. Phys. **134**, 144107 (2011)] is employed to treat the collisional energy transfer and the ro-vibrational energy flow in a recombination reaction that forms ozone. Assumption is that the van der Waals states of ozone are formed in the O + O_{2} collisions, and then stabilized into the states of covalent well by collisions with bath gas. Cross sections for collision induced dissociation of van der Waals states of ozone, for their stabilization into the covalent well, and for their survival in the van der Waals well are computed. The role these states may play in the kinetics of ozone formation is discussed.

This research was supported by the National Science Foundation (NSF) Atmospheric Chemistry Program, Division of Atmospheric Sciences, Grant No. 0842530. This research used resources of the National Energy Research Scientific Computing Center, which is supported by the Office of Science of the U.S. Department of Energy under Contract No. DE-AC02–05CH11231.

I. INTRODUCTION

II. THEORETICAL FRAMEWORK

III. RESULTS AND DISCUSSION

IV. KINETICS OF RECOMBINATION

V. CONCLUSIONS

### Key Topics

- Ozone
- 102.0
- Energy transfer
- 33.0
- Dissociation
- 23.0
- Vibrational states
- 11.0
- Elasticity
- 9.0

## Figures

Spectrum of states of ^{16}O^{18}O^{16}O with *J* = 19 (*K* _{a} = 4, *K* _{b} = 12) near the dissociation threshold. Slices of PES along two channels show the main covalent well and two shallow vdW wells. The vibrational character of states can be identified by their position in one of the wells. In this model the rotational and bending motions are treated adiabatically.

Spectrum of states of ^{16}O^{18}O^{16}O with *J* = 19 (*K* _{a} = 4, *K* _{b} = 12) near the dissociation threshold. Slices of PES along two channels show the main covalent well and two shallow vdW wells. The vibrational character of states can be identified by their position in one of the wells. In this model the rotational and bending motions are treated adiabatically.

(a) Dissociation probability as a function of impact parameter for the initial state 53. Each dot corresponds to one quantum-classical trajectory; 13500 randomly sampled trajectories are used. (b) Illustration of convergence of the dissociation cross sections for the initial states 51, 53, and 54 as the maximum impact parameter is increased.

(a) Dissociation probability as a function of impact parameter for the initial state 53. Each dot corresponds to one quantum-classical trajectory; 13500 randomly sampled trajectories are used. (b) Illustration of convergence of the dissociation cross sections for the initial states 51, 53, and 54 as the maximum impact parameter is increased.

Total energy transfer as a function of impact parameter for the initial state 51. Color shows probability of the process which increases ten orders of magnitude from violet to red. (a) Linear energy scale is employed. (b) Same data, but logarithmic scale for |Δ*E*| is employed in order to magnify the low energy part of the distribution.

Total energy transfer as a function of impact parameter for the initial state 51. Color shows probability of the process which increases ten orders of magnitude from violet to red. (a) Linear energy scale is employed. (b) Same data, but logarithmic scale for |Δ*E*| is employed in order to magnify the low energy part of the distribution.

Rotational energy transfer in the O_{3} + Ar collisions as a function of angular momentum transfer. Initial state is state 51. Each dot corresponds to one quantum-classical trajectory; 13500 randomly sampled trajectories are used. Two groups of dots are clearly identified. Three lines correspond to analytic rigid-rotor models with different moments of inertia (see text). Three inserts show corresponding rotations of O_{3}.

Rotational energy transfer in the O_{3} + Ar collisions as a function of angular momentum transfer. Initial state is state 51. Each dot corresponds to one quantum-classical trajectory; 13500 randomly sampled trajectories are used. Two groups of dots are clearly identified. Three lines correspond to analytic rigid-rotor models with different moments of inertia (see text). Three inserts show corresponding rotations of O_{3}.

Vibrational energy transfer as a function of (a) angular momentum transfer and (b) impact parameter. Color shows probability of the process which increases ten orders of magnitude from violet to red. Initial state is state 51. The quantized vibrational spectrum of O_{3} is clearly identified.

Vibrational energy transfer as a function of (a) angular momentum transfer and (b) impact parameter. Color shows probability of the process which increases ten orders of magnitude from violet to red. Initial state is state 51. The quantized vibrational spectrum of O_{3} is clearly identified.

The energy transfer functions expressed as the differential (over energy) cross sections. Three frames correspond to three initial states. Transition and stabilization cross sections, as defined in the text, are shown as black circles and red dots, respectively. Presence of the vdW states in the range −150 < *E* < +500 cm^{−1} lifts circles with respect to the dots by several orders of magnitude. Outside of this range circles and dots coincide. Fit of each wing by the exponential model is shown as solid line. The elastic scattering peak is seen in each frame.

The energy transfer functions expressed as the differential (over energy) cross sections. Three frames correspond to three initial states. Transition and stabilization cross sections, as defined in the text, are shown as black circles and red dots, respectively. Presence of the vdW states in the range −150 < *E* < +500 cm^{−1} lifts circles with respect to the dots by several orders of magnitude. Outside of this range circles and dots coincide. Fit of each wing by the exponential model is shown as solid line. The elastic scattering peak is seen in each frame.

## Tables

Cross sections for stabilization, dissociation, and survival (as defined in the text) for three initial states.

Cross sections for stabilization, dissociation, and survival (as defined in the text) for three initial states.

Parameters for single and double exponential models used to fit each wing of the energy transfer functions in Fig. 6.

Parameters for single and double exponential models used to fit each wing of the energy transfer functions in Fig. 6.

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