Ultrafast nonadiabatic electron dynamics in photoexcited C60: A comparative study among DFT exchange-correlation functionals

TL;DR

This study compares the effects of different DFT exchange-correlation functionals on ultrafast nonadiabatic electron dynamics in photoexcited C60, revealing qualitative similarities and model-dependent differences in population dynamics and providing insights for spectroscopic probing.

Contribution

It systematically evaluates how various DFT functionals influence nonadiabatic electron dynamics in C60, aiding method optimization and experimental validation.

Findings

All three functionals produce similar unoccupied band structures.

Differences in population dynamics depend on the functional used.

Results suggest a universal dependence on unoccupied band structure.

Abstract

The non-radiative electron-relaxation dynamics in C$_{60}$ molecule is studied after selective initial photoexcitations. The methodology includes nonadibabtic molecular simulation combined with time-dependent density functional theory (DFT) and semi-classical surface hopping approach. Results of treating the DFT exchange-correlation (xc) interaction by the non-empirical Perdew-Burke-Ernzerhof (PBE), hybrid PBE0, and hybrid Becke 3-parameter Lee-Yang-Parr (B3LYP) functional are compared. Even though some differences in the details are found, all three functionals produce qualitatively similar unoccupied band structures in the ground state. The model-dependent differences in the ultrafast population dynamics, including the occurrences of transient entrapment of population, are studied systematically. The trend of the results demonstrates a universal dependence on the structure of unoccupied band offering a spectroscopic route to probe this structure. Results can be verified, as well as the best xc model for quantitative accuracy can be determined, by comparing with ultrafast transient absorption or time-resolved photoelectron spectroscopy measurements. From the computational standpoint, the study facilitates method optimization to simulate nonadiabatic relaxation dynamics in technologically important fullerene derivatives.