ChemRxiv
These are preliminary reports that have not been peer-reviewed. They should not be regarded as conclusive, guide clinical practice/health-related behavior, or be reported in news media as established information. For more information, please see our FAQs.
paper_HHG_pauletti.pdf (1.95 MB)

Role of Exchange and Correlation in High-Harmonic Generation Spectra of H2, N2 and CO2: Real-Time Time-Dependent Electronic-Structure Approaches

preprint
submitted on 23.10.2020, 21:40 and posted on 28.10.2020, 08:33 by Emanuele Coccia, Eleonora Luppi, Carlo Federico Pauletti

This study arises from the attempt to answer the following question: how different descriptions of electronic exchange and correlation affect the high-harmonic generation (HHG) spectroscopy of H2, N2 and CO2 molecules? We compare HHG spectra for H2, N2 and CO2 with different ab initio electronic structures methods: real-time time-dependent configuration interaction (RT-TDCIS) and real-time time-dependent density functional theory (RT-TDDFT) using truncated basis sets composed of correlated wave functions expanded on Gaussian basis sets. In the framework of RT-TDDFT, we employ PBE and LC-ωPBE functionals. We study HHG spectroscopy by disentangling the effect of electronic exchange and correlation. We first analyse the electronic exchange alone and in the case of RT-TDDFT with LC-ωPBE, we use ω = 0.3 and ω = 0.4 to tune the percentage of long-range Hartree-Fock exchange and of short-range exchange PBE. Then, we added the correlation as described by PBE functional. All the methods give very similar HHG spectra and they seem not to be particularly sensitive to the different description of exchange and correlation or to the correct asymptotic behaviour of the Coulomb potential. Despite this general trend, some differences are found in the region connecting the cutoff and the background. Here, the harmonics can be resolved with different accuracy depending on the theoretical schemes used. We believe that the investigation of the molecular continuum and its coupling with strong fields merits further theoretical investigations in the next future.

History

Email Address of Submitting Author

ecoccia@units.it

Institution

University of Trieste

Country

Italy

ORCID For Submitting Author

0000-0003-3389-0989

Declaration of Conflict of Interest

No conflict.

Exports

Logo branding

Exports