Describing the photo-isomerization of a retinal chromophore model with coupled and quantum trajectories

Abstract

The exact factorization of the electron-nuclear wavefunction is applied to the study of the photo- isomerization of a retinal chromophore model. We describe such an ultrafast nonadiabatic process by analyzing the time-dependent potentials of the theory and by mimicking nuclear dynamics with quantum and coupled trajectories. The time-dependent vector and scalar potentials are the signature of the exact factorization, as they guide nuclear dynamics by encoding the complete electronic dynamics and including excited-state effects. Analysis of the potentials is, thus, essential – when possible – to predict the time-dependent behavior of the system of interest. In this work, we employ the exact time-dependent potentials, available for the numerically-exactly solvable model used here, to propagate quantum nuclear trajectories representing the isomerization reaction of the retinal chromophore. The quantum trajectories are the best possible trajectory-based description of the reaction when using the exact-factorization formalism, and thus allow us to assess the performance of the coupled-trajectory, fully approximate, schemes derived from the exact-factorization equations.

Adiabatic and Nonadiabatic Dynamics with Interacting Quantum Trajectories

“…In past years, such QTMs have been used to describe the quantum nuclear behaviour of different model [16][17][18][19][20][21][22][23][24] and molecular systems. [25][26][27][28] In this work, our aim is to focus on the theoretical and numerical aspects of one particular quantum trajectory formalism, and its application to adiabatic and nonadiabatic problems.…”