Mixed quantum-classical simulations of intersystem crossing in the exit channel and vibrational adaptive sampling configuration interaction
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A computational study using mixed quantum-classical surface hopping simulations was performed for the reaction of O(3P) with dimethylamine and trimethylamine. These reactions produce an OH radical and while the OH radical is in the exit channel of the reaction, the triplet excited electronic state can undergo a transition via intersystem crossing (ISC) to a singlet state. This occurs near the point where the potential energy curves for the two excited states cross due to spin-orbit coupling (SOC). The simulations used the trajectory surface-hopping method to model these ISC processes. These simulations were performed utilizing the SHARC code and methodology, which can include arbitrary couplings between the Born-Oppenheimer potential energy surfaces (PES). The calculations on these systems were performed with the aug-cc-pVDZ basis set and the CAM-B3LYP exchange-correlation functional. We computed the ratio of tripletto- singlet states within the exit channel as a function of time to obtain the triplet-to-singlet crossing rate. For both systems significant ISC from the triplet surface to the singlet surface is observed, which provides further evidence that ISC can occur in the exit channel for these systems.
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M.S.