Significant contributions of second-order exchange terms in <i>GW</i> electron–hole interaction kernel for charge-transfer excitations
-
- Satoka Yamada
- Department of Applied Chemistry and Biochemical Engineering, Graduate School of Engineering, Shizuoka University , 3-5-1 Johoku, Hamamatsu, Shizuoka 432-8561, Japan
-
- Yoshifumi Noguchi
- Department of Applied Chemistry and Biochemical Engineering, Graduate School of Engineering, Shizuoka University , 3-5-1 Johoku, Hamamatsu, Shizuoka 432-8561, Japan
書誌事項
- 公開日
- 2023-12-15
- 資源種別
- journal article
- DOI
-
- 10.1063/5.0178723
- 公開者
- AIP Publishing
この論文をさがす
説明
<jats:p>The GW electron–hole interaction kernel, which includes two second-order exchange terms in addition to the first-order direct and exchange terms considered in the conventional GW + Bethe–Salpeter method, is applied to 10 two-molecular systems and six thermally activated delayed fluorescence (TADF) molecules in which inter- and intramolecular charge transfer excitations are expected to occur. The contributions of the two second-order exchange terms are almost zero for intermolecular charge transfer excitations and ∼0.75 eV for intramolecular charge transfer excitations according to our exciton analysis method with exciton wave functions. For TADF molecules, we found that the second-order exchange terms are more significant than the first-order exchange terms, and the contributions—even for local-type and delocalized-type excitations—are not negligibly small. We revealed that the two second-order exchange terms are proportional to the molecular size, the exciton binding energy, and the electron–hole overlap strength for intramolecular charge-transfer excitations. We believe that our findings are indispensable for further considerations of the GW method in the future.</jats:p>
収録刊行物
-
- The Journal of Chemical Physics
-
The Journal of Chemical Physics 159 (23), 234105-, 2023-12-15
AIP Publishing
