Accurate Prediction of the S 1 Excitation Energy in Solvated Azobenzene Derivatives via Embedded Orbital-Tuned Bethe-Salpeter Calculations - Archive ouverte HAL Accéder directement au contenu
Article Dans Une Revue Journal of Chemical Theory and Computation Année : 2020

Accurate Prediction of the S 1 Excitation Energy in Solvated Azobenzene Derivatives via Embedded Orbital-Tuned Bethe-Salpeter Calculations

Résumé

By employing the Bethe-Salpeter formalism coupled 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 adopting an orbital-tuning approach via the global hybrid functional, PBEh, yielding an environment-consistent ionization potential. The vertical excitation energy of 20 azo molecules are predicted 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.

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Chimie
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Dates et versions

hal-02503936 , version 1 (08-12-2020)

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Aseem Rajan Kshirsagar, Gabriele D’avino, Xavier Blase, Jing Li, Roberta Poloni. Accurate Prediction of the S 1 Excitation Energy in Solvated Azobenzene Derivatives via Embedded Orbital-Tuned Bethe-Salpeter Calculations. Journal of Chemical Theory and Computation, 2020, 16 (4), pp.2021-2027. ⟨10.1021/acs.jctc.9b01257⟩. ⟨hal-02503936⟩
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