Relativistic fully self-consistent $GW$ for molecules: Total energies and ionization potentials
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| Formato: | Preprint |
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2024
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| author | Abraham, Vibin Harsha, Gaurav Zgid, Dominika |
| author_facet | Abraham, Vibin Harsha, Gaurav Zgid, Dominika |
| contents | The fully self-consistent $GW$ (sc$GW$) method with the iterative solution of Dyson equation provides a consistent approach for describing the ground and excited states without any dependence on the mean-field reference. In this work, we present a relativistic version of sc$GW$ for molecules containing heavy element using the exact two-component (X2C) Coulomb approximation. We benchmark $\texttt{SOC-81}$ dataset containing closed shell heavy elements for the first ionization potential using the fully self-consistent $GW$ as well as one-shot $GW$. The self-consistent $GW$ provides superior result compared to $G_0W_0$ with PBE reference and comparable to $G_0W_0$ with PBE0 while also removing the starting point dependence. The photoelectron spectra obtained at the X2C level demonstrate very good agreement with experimental spectra. We also observe that sc$GW$ provides very good estimation of ionization potential for the inner $d$ shell orbitals. Additionally, using the well conserved total energy, we investigate the equilibrium bond length and harmonic frequencies of few halogen dimers using sc$GW$. Overall, our findings demonstrate the applicability of the fully self-consistent $GW$ method for accurate ionization potential, photoelectron spectra and total energies in finite systems with heavy elements with a reasonable computational scaling. |
| format | Preprint |
| id |
arxiv_https___arxiv_org_abs_2401_11303 |
| institution | arXiv |
| publishDate | 2024 |
| record_format | arxiv |
| spellingShingle | Relativistic fully self-consistent $GW$ for molecules: Total energies and ionization potentials Abraham, Vibin Harsha, Gaurav Zgid, Dominika Chemical Physics The fully self-consistent $GW$ (sc$GW$) method with the iterative solution of Dyson equation provides a consistent approach for describing the ground and excited states without any dependence on the mean-field reference. In this work, we present a relativistic version of sc$GW$ for molecules containing heavy element using the exact two-component (X2C) Coulomb approximation. We benchmark $\texttt{SOC-81}$ dataset containing closed shell heavy elements for the first ionization potential using the fully self-consistent $GW$ as well as one-shot $GW$. The self-consistent $GW$ provides superior result compared to $G_0W_0$ with PBE reference and comparable to $G_0W_0$ with PBE0 while also removing the starting point dependence. The photoelectron spectra obtained at the X2C level demonstrate very good agreement with experimental spectra. We also observe that sc$GW$ provides very good estimation of ionization potential for the inner $d$ shell orbitals. Additionally, using the well conserved total energy, we investigate the equilibrium bond length and harmonic frequencies of few halogen dimers using sc$GW$. Overall, our findings demonstrate the applicability of the fully self-consistent $GW$ method for accurate ionization potential, photoelectron spectra and total energies in finite systems with heavy elements with a reasonable computational scaling. |
| title | Relativistic fully self-consistent $GW$ for molecules: Total energies and ionization potentials |
| topic | Chemical Physics |
| url | https://arxiv.org/abs/2401.11303 |