Modeling of High-Harmonic Generation in the C₆₀ Fullerene Using Ab Initio, DFT-Based, and Semiempirical Methods

Abstract

We report calculations of the high-harmonic generation spectra of the C60 fullerene molecule carried out by employing a diverse set of real-time time-dependent quantum chemical methods. All methodologies involve expanding the propagated electronic wave function in bases consisting of the ground and singly excited time-independent eigenstates obtained through the solution of the corresponding linear-response equations. We identify the correlation and exchange effect in the spectra by comparing the results from methods relying on the Hartree–Fock reference determinant with those obtained using approaches based on the density functional theory with different exchange–correlation functionals. The effect of the full random-phase approximation treatment of the excited electronic states is also analyzed and compared with the configuration interaction singles and the Tamm–Dancoff approximation. We also showcase the fact that the real-time extension of the semiempirical method INDO/S can be effectively applied for an approximate description of laser-driven dynamics in large systems.

Virtual Special Issue on Attosecond Chemistry

“…Theoretical methods are also seeking to understand the role of electron correlation in HHG from molecules. Li et al have done so in small molecules such as H 2 , LiH, and N 2 , and Woźniak et al studied the fullerene C 60 by comparing HHG spectra obtained from ab initio, density functional theory and semiempirical methods …”