Quantum Dynamics Simulation of Doublet Excitation and Magnetic Field Effect in Neutral Radical Materials.

Abstract

The photon absorption and the relevant magnetic field effect of a doublet in neutral radical materials are investigated by combining the density functional theory and the variational quantum dynamics with Davydov ansatz. The doublet is a perfect model system to study the full-quantum dynamics of a two-level system coupling to a realistic molecular vibrational environment. In this work, we simulate the optical absorption spectroscopy of the neutral radical material, (4-N-carbazolyl-2,6-dichlorophenyl)bis(2,4,6-trichlorophenyl)-methyl, and find a good agreement with experiments for both highest occupied molecular orbital-singly occupied molecular orbital (SOMO) and SOMO-lowest unoccupied molecular orbital transitions. The nontrivial role of the intramolecular vibronic couplings is comprehensively discussed with separate spectroscopy and population dynamics, suggesting different contributions and the long time scale effect stemming from the vibrations, according to different symmetries. On the basis of the model, an applied magnetic field is taken into account to qualitatively investigate its magnetic properties in a dynamics manner, leading to a result which can be described by a sum of Lorentzian functions.