Particle-Particle Random Phase Approximation for Predicting Correlated Excited States of Point Defects
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arXiv
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2024
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| author | Li, Jiachen Jin, Yu Yu, Jincheng Yang, Weitao Zhu, Tianyu |
| author_facet | Li, Jiachen Jin, Yu Yu, Jincheng Yang, Weitao Zhu, Tianyu |
| contents | The particle-particle random phase approximation (ppRPA) within the hole-hole channel was recently proposed as an efficient tool for computing excitation energies of point defects in solids [J. Phys. Chem. Lett. 2024, 15, 2757-2764]. In this work, we investigate the application of ppRPA within the particle-particle channel for predicting correlated excited states of point defects, including the carbon-vacancy (VC) in diamond, the oxygen-vacancy (VO) in magnesium oxide (MgO), and the carbon dimer defect (C$_{\text{B}}$C$_{\text{N}}$) in two-dimensional hexagonal boron nitride (h-BN). Starting from a density functional theory calculation of the ($N-2$)-electron ground state, vertical excitation energies of the $N$-electron system are obtained as the differences between the two-electron addition energies. We show that active-space ppRPA with the B3LYP functional yields accurate excitation energies, with errors mostly smaller than 0.1 eV for tested systems compared to available experimental values. We further develop a natural transition orbital scheme within ppRPA, which provides insights into the multireference character of defect states. This study, together with our previous work, establishes ppRPA as a low-cost and accurate method for investigating excited-state properties of point defect systems. |
| format | Preprint |
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arxiv_https___arxiv_org_abs_2406_18515 |
| institution | arXiv |
| publishDate | 2024 |
| record_format | arxiv |
| spellingShingle | Particle-Particle Random Phase Approximation for Predicting Correlated Excited States of Point Defects Li, Jiachen Jin, Yu Yu, Jincheng Yang, Weitao Zhu, Tianyu Chemical Physics Materials Science Computational Physics The particle-particle random phase approximation (ppRPA) within the hole-hole channel was recently proposed as an efficient tool for computing excitation energies of point defects in solids [J. Phys. Chem. Lett. 2024, 15, 2757-2764]. In this work, we investigate the application of ppRPA within the particle-particle channel for predicting correlated excited states of point defects, including the carbon-vacancy (VC) in diamond, the oxygen-vacancy (VO) in magnesium oxide (MgO), and the carbon dimer defect (C$_{\text{B}}$C$_{\text{N}}$) in two-dimensional hexagonal boron nitride (h-BN). Starting from a density functional theory calculation of the ($N-2$)-electron ground state, vertical excitation energies of the $N$-electron system are obtained as the differences between the two-electron addition energies. We show that active-space ppRPA with the B3LYP functional yields accurate excitation energies, with errors mostly smaller than 0.1 eV for tested systems compared to available experimental values. We further develop a natural transition orbital scheme within ppRPA, which provides insights into the multireference character of defect states. This study, together with our previous work, establishes ppRPA as a low-cost and accurate method for investigating excited-state properties of point defect systems. |
| title | Particle-Particle Random Phase Approximation for Predicting Correlated Excited States of Point Defects |
| topic | Chemical Physics Materials Science Computational Physics |
| url | https://arxiv.org/abs/2406.18515 |