Ab initio nonadiabatic dynamics study of ultrafast radiationless decay over conical intersections illustrated on the Na3F cluster

Roland Mitrić, Vlasta Bonačić-Koutecký, Jiří Pittner, Hans Lischka

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Abstract

We present a theoretical approach for the ultrafast nonadiabatic dynamics based on the ab initio molecular dynamics carried out "on the fly" in the framework of the configuration interaction method combined with Tully's surface hopping algorithm for nonadiabatic transitions. This approach combined with our Wigner distribution approach allows us to perform accurate simulations of femtosecond pump-probe spectra in the systems where radiationless transitions among electronic states take place. In this paper we illustrate this by theoretical simulation of ultrafast processes and nonradiative relaxation in the Na3F cluster, involving three excited states and the ground electronic state. Furthermore, we show that our accurate simulation of the photoionization pump-probe spectrum is in full agreement with the experimental signal. Based on the nonadiabatic dynamics at high level of accuracy and taking into account all degrees of freedom, the nonradiative lifetime for the 1 1B, excited state of Na3F has been determined to be ∼900 fs.

Original languageEnglish
Article number024303
JournalJournal of Chemical Physics
Volume125
Issue number2
DOIs
StatePublished - 2006

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