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Classical dynamics of state-resolved hyperthermal O(

^{3}P) + H

_{2}O(

^{1}A

_{1}) collisions

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10.1063/1.4790589

### Abstract

Classical dynamics calculations are performed for O(^{3}P) + H_{2}O(^{1}A_{1}) collisions from 2 to 10 km s^{‑1} (4.1–101.3 kcal mol^{−1}), focusing on product internal energies. Several methods are used to produce ro-vibrationally state-resolved product cross sections and to enforce zero-point maintenance from analysis of the classical trajectories. Two potential energy surfaces are used: (1) a recently developed set of global reactive surfaces for the three lowest triplet states which model OH formation, H elimination to make H + OOH, O-atom exchange, and collisional excitation and (2) a non-reactive surface used in past classical and quantum collision studies. Comparisons to these previous studies suggest that for H_{2}O vibrational excitation, classical dynamics which include Gaussian binning procedures and/or selected zero-point maintenance algorithms can produce results which approximate quantum scattering cross sections fairly well. Without these procedures, the classical cross sections can be many orders of magnitude greater than the quantum cross sections for exciting the bending vibration of H_{2}O, especially near threshold. The classical cross section over-estimate is due to energy borrowing from stretching modes which dip below zero-point values. For results on the reactive surfaces, the present calculations show that at higher velocities there is an unusually large amount of product internal excitation. For OOH, where 40% of available collision energy goes into internal motion, the excited product vibrational and rotational energy distributions are relatively flat and values of the OOH rotational angular momentum exceed J = 100. Other product channel distributions show an exponential fall-off with energy consistent with an energy gap law. The present detailed distributions and cross sections can serve as a guide for future hyperthermal measurements of this system.

© 2013 American Institute of Physics

Received 31 October 2012
Accepted 22 January 2013
Published online 15 February 2013

Acknowledgments: The authors acknowledge support under Contract No. W9113M-10-C-0082. We also acknowledge George Schatz, Northwestern University, for technical help with the BRSG surface. Finally, we acknowledge Tom Smith of AFRL for technical guidance.

Article outline:

I. INTRODUCTION

II. METHODS

A. Potential surfaces

B. Classical dynamics formulation

1. Separation of rotational and vibrational motion

2. Determination of quantum numbers

3. Zero-point maintenance

4. Histogram and Gaussian binning

5. Rotational quantum numbers and diatomic vibration

C. Classical dynamics calculations

III. QCT RESULTS USING THE BRSG SURFACE

IV. QCT RESULTS USING THE CBBB SURFACES

A. Ro-vibrational excitation of H_{2}O

B. Reactive cross sections

1. OH + OH reaction

2. OOH + H reaction

3. Rate constant calculations

V. CONCLUSIONS

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/content/aip/journal/jcp/138/7/10.1063/1.4790589

2013-02-15

2014-04-18

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