Modeling of High-Harmonic Generation in the C 60 Fullerene Using Ab Initio, DFT-Based, and Semiempirical Methods

• Published in: The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Molecules, spectroscopy, kinetics, environment, & general theory, 2024-04, Vol.128 (14), p.2683-2702
• Main Authors: Woźniak, Aleksander P, Moszyński, Robert
• Format: Article
• Language: English
• ISSN: 1089-5639; 1520-5215
• DOI: 10.1021/acs.jpca.3c07865

We report calculations of the high-harmonic generation spectra of the C 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.