Intramolecular and reactive dynamics of OH-overtone excited HOOH (D): A classical trajectory study on a quasiseparable potential surface

Abstract Classical trajectories are used to study the intramolecular dynamics of the OH overtone (νOH= 5–9) induced unimolecular dissociation of HOOH (D). Detailed examination of the reaction dynamics sensitivity to variations of a simple quasiseparable potential energy surface, overall molecular rotation and initial condition selection are investigated. The results clearly show the importance of accurate potential energy representation and provide strong evidence toward which type(s) of interactions are most essential to describe the reaction dynamics. In particular, the stretch-bend coupling is found to play an important role in the rotation-vibration dynamics of HOOH (D).

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