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These are preliminary reports that have not been peer-reviewed.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.
1/1
2 files
0/0

Accurate Prediction of the S1 Excitation Energy in Solvated Azobenzene Derivatives via Embedded Orbital-Tuned Bethe-Salpeter Calculations

preprint
submitted on 29.11.2019 and posted on 09.12.2019 by Aseem Rajan Kshirsagar, Gabriele D'Avino, Xavier Blase, Jing Li, Roberta Poloni
By employing the Bethe-Salpeter formalism with a non-equilibrium embedding scheme, we demonstrate that the paradigmatic case of S1 band separation between cis and trans in azobenzene derivatives can be computed with excellent accuracy compared to experimental optical spectra. Besides embedding, we show that the choice of the Kohn-Sham exchange correlation functional for DFT is critical, despite the iterative convergence of GW quasiparticle energies. We address this by using a global hybrid functional, PBEh, with the amount of exact exchange fulfilling the Koopman’s theorem for DFT hence yielding an environment-consistent ionization potential.
This method yields the first vertical excitation energy of 20 azo molecules with a mean absolute error as low as 0.06 eV, up to three times smaller compared to standard functionals such as M06-2X and PBE0, and five times smaller compared to recent TDDFT results.

Funding

ANR ANR-15-CE06-0003-01

History

Email Address of Submitting Author

roberta.poloni@simap.grenoble-inp.fr

Institution

CNRS

Country

France

ORCID For Submitting Author

0000-0002-5379-3839

Declaration of Conflict of Interest

The authors declare no conflict of interests

Exports