Why the lowest electronic excitations of rhodamines are overestimated by time-dependent density functional theory
文献类型：期刊论文
| 作者 | Zhou, Panwang
|
| 刊名 | INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY
 |
| 出版日期 | 2018-12-05 |
| 卷号 | 118期号:23页码:11 |
| 关键词 | ADC(2) cyanine dyes rhodamine dyes TDDFT XMCQDPT2 |
| ISSN号 | 0020-7608 |
| DOI | 10.1002/qua.25780 |
| 通讯作者 | Zhou, Panwang(pwzhou@dicp.ac.cn) |
| 英文摘要 | Rhodamines are widely used as laser dyes and fluorescent probes due to their excellent photophysical and photochemical properties. Previous theoretical studies have shown that the lowest excitation energies of rhodamines are overestimated systematically by time-dependent density functional theory (TDDFT). In this study, we first perform a TDDFT benchmark study with 21 exchange-correlation functionals (XCFs) on a series of rhodamines and assess the performance of different types of functional in predicting the lowest excitation energies of rhodamines. Statistical results reveal that the fraction of Hartree-Fock exchange (HFX) included in the XCF is a key parameter. Pure functionals without HFX offer the best performance, with the mean absolute error (MAE) of approximately 0.1 eV. However, they provide a wrong order of the lowest n pi* and pi pi* states and suffer from charge-transfer contamination problem for rhodamine dyes (RDs) in zwitterionic form. Among the other tested functionals, popular global hybrid functional B3LYP delivers the smallest MAE of 0.36 eV. We then perform calculations with second-order algebraic diagrammatic construction and extended multiconfiguration quasi-degenerate perturbation theory at second-order of PT expansion methods. Remarkably accurate results are obtained. We confirm that the reason for the overestimation of the lowest excitation energies of RDs by TDDFT method should be similar to that of cyanine dyes, and that double excitations contribute to this systematic deviation. |
| WOS关键词 | CHARGE-TRANSFER EXCITATIONS ; EXCITED-STATES ; TD-DFT ; CORRELATION-ENERGY ; THERMOCHEMICAL KINETICS ; POLARIZATION PROPAGATOR ; FLUORESCENCE LIFETIMES ; OPTICAL SIGNATURES ; HYPOCHLOROUS ACID ; QUANTUM YIELDS |
| 资助项目 | National Natural Science Foundation of China[21773238] |
| WOS研究方向 | Chemistry ; Mathematics ; Physics |
| 语种 | 英语 |
| WOS记录号 | WOS:000449631100003 |
| 出版者 | WILEY |
| 资助机构 | National Natural Science Foundation of China ; National Natural Science Foundation of China ; National Natural Science Foundation of China ; National Natural Science Foundation of China ; National Natural Science Foundation of China ; National Natural Science Foundation of China ; National Natural Science Foundation of China ; National Natural Science Foundation of China |
| 源URL | [http://cas-ir.dicp.ac.cn/handle/321008/166680]  |
| 专题 | 大连化学物理研究所_中国科学院大连化学物理研究所 |
| 通讯作者 | Zhou, Panwang |
| 作者单位 | Chinese Acad Sci, Dalian Inst Chem Phys, State Key Lab Mol React Dynam, Dalian 116023, Liaoning, Peoples R China |
| 推荐引用方式 GB/T 7714 | Zhou, Panwang. Why the lowest electronic excitations of rhodamines are overestimated by time-dependent density functional theory[J]. INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY,2018,118(23):11. |
| APA | Zhou, Panwang.(2018).Why the lowest electronic excitations of rhodamines are overestimated by time-dependent density functional theory.INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY,118(23),11. |
| MLA | Zhou, Panwang."Why the lowest electronic excitations of rhodamines are overestimated by time-dependent density functional theory".INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY 118.23(2018):11. |
入库方式： OAI收割
来源：大连化学物理研究所
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