The Role of dissociation channels of excited electronic states in quantum optimal control of ozone isomerization; A Three-state dynamical model

オゾン分子異性化の量子最適制御における電子励起状態の解離チャンネルの役割; 三状態動的モデル

黒崎 譲; Ho, T.-S.*; Rabitz, H.*

Kurosaki, Yuzuru; Ho, T.-S.*; Rabitz, H.*

The prospect of performing the open cyclic ozone isomerization has attracted much research attention. Here we explore this consideration theoretically by performing quantum optimal control calculations to demonstrate the important role that excited-state dissociation channels could play in the isomerization transformation. In the calculations we use a three-state, one-dimensional dynamical model constructed from the lowest five A' potential energy curves obtained with high-level calculations. Besides the laser field-dipole couplings between all three states, this model also includes the diabatic coupling between the two excited states at an avoided crossing leading to competing dissociation channels that can further hinder the isomerization process. The present three-state optimal control simulations examine two possible control pathways previously considered in a two-state model, and reveal that only one of the pathways is viable, achieving a robust 95% yield to the cyclic target in the three-state model.