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Abstract:
We utilize the exact factorization of the electron-nuclear wave function [Abedi et al., PRL 105 123002 (2010)] to illuminate several aspects of laser-driven molecular dynamics in intense femtosecond laser pulses. Above factorization allows for a splitting of the full molecular wave function and leads to a time-dependent Schrödinger equation for the nuclear subsystem alone which is exact in the sense that the absolute square of the corresponding, purely nuclear, wave function yields the exact nuclear N-body density of the full electron-nuclear system. As one remarkable feature, this factorization provides the exact classical force, the force which contains the highest amount of electron-nuclear correlations that can be retained in the quantum-classical limit of the electron-nuclear system. We re-evaluate the classical limit of the nuclear Schrödinger equation from the perspective of the exact factorization, and address the long-standing question of the validity of the popular quantum-classical surface hopping approach in laserdriven cases. In particular, our access to the exact classical force allows for an elaborate evaluation of the various and completely different potential energy surfaces frequently applied in surface hopping calculations. The highlight of this work consists in a generalization of the exact factorization and its application to the laser-driven molecular wave function in the Floquet picture, where the molecule and the laser form an united quantum system exhibiting its own Hilbert space. This particular factorization enables us to establish an analytic connection between the exact nuclear force and Floquet potential energy surfaces. Complementing above topics, we combine different well-known and proven methods to give a systematic study of molecular dissociation mechanisms for the complicated electric fields provided by modern attosecond laser technology.
