title: Interplay of radiative and nonradiative transitions in surface hopping with radiation-molecule interactions.
abstract: We implemented a method for the treatment of field induced transitions in trajectory surface hopping simulations, in the framework of the local diabatization scheme, especially suited for on-the-fly dynamics. The method is applied to a simple one-dimensional model with an avoided crossing and compared with quantum wavepacket dynamics. The results show the importance of introducing a proper decoherence correction to surface hopping, in order to obtain meaningful results. Also the energy conservation policy of standard surface hopping must be revised: in fact, the quantum wavepacket energetics is well reproduced if energy absorption/emission is allowed for in the hops determined by radiation-molecule coupling. To our knowledge, this is the first time the issues of decoherence and energy conservation have been analyzed in depth to devise a mixed quantum-classical method for dynamics with molecule-field interactions.
authors: Departamento de Química-Física I, Universidad Complutense de Madrid, 28040 Madrid, Spain.
authors: Juan José
authors: JJ
authors: Bajo
authors: Università di Pisa, Dipartimento di Chimica e Chimica Industriale, via Risorgimento 35, 56126 Pisa, Italy.
authors: Giovanni
authors: G
authors: Granucci
authors: Università di Pisa, Dipartimento di Chimica e Chimica Industriale, via Risorgimento 35, 56126 Pisa, Italy.
authors: Maurizio
authors: M
authors: Persico