Assessment of Ab Initio and Density Functional Theory Methods for the Excitations of Donor-Acceptor Complexes: The Case of the Benzene-Tetracyanoethylene Model
The understanding of the excited-state properties of electron donors, acceptors and their interfaces in organic optoelectronic devices is a fundamental issue for their performance optimization. In order to obtain a balanced description of the different excitation types for electron-donor-acceptor sy...
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MDPI AG
2018-04-01
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| Series: | International Journal of Molecular Sciences |
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| author | Peng Xu Cai-Rong Zhang Wei Wang Ji-Jun Gong Zi-Jiang Liu Hong-Shan Chen |
| author_facet | Peng Xu Cai-Rong Zhang Wei Wang Ji-Jun Gong Zi-Jiang Liu Hong-Shan Chen |
| author_sort | Peng Xu |
| collection | DOAJ |
| description | The understanding of the excited-state properties of electron donors, acceptors and their interfaces in organic optoelectronic devices is a fundamental issue for their performance optimization. In order to obtain a balanced description of the different excitation types for electron-donor-acceptor systems, including the singlet charge transfer (CT), local excitations, and triplet excited states, several ab initio and density functional theory (DFT) methods for excited-state calculations were evaluated based upon the selected model system of benzene-tetracyanoethylene (B-TCNE) complexes. On the basis of benchmark calculations of the equation-of-motion coupled-cluster with single and double excitations method, the arithmetic mean of the absolute errors and standard errors of the electronic excitation energies for the different computational methods suggest that the M11 functional in DFT is superior to the other tested DFT functionals, and time-dependent DFT (TDDFT) with the Tamm–Dancoff approximation improves the accuracy of the calculated excitation energies relative to that of the full TDDFT. The performance of the M11 functional underlines the importance of kinetic energy density, spin-density gradient, and range separation in the development of novel DFT functionals. According to the TDDFT results, the performances of the different TDDFT methods on the CT properties of the B-TCNE complexes were also analyzed. |
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| issn | 1422-0067 |
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| last_indexed | 2024-04-13T07:12:20Z |
| publishDate | 2018-04-01 |
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| spelling | doaj.art-479d112b96054ca1b27a06d3100369942022-12-22T02:56:50ZengMDPI AGInternational Journal of Molecular Sciences1422-00672018-04-01194113410.3390/ijms19041134ijms19041134Assessment of Ab Initio and Density Functional Theory Methods for the Excitations of Donor-Acceptor Complexes: The Case of the Benzene-Tetracyanoethylene ModelPeng Xu0Cai-Rong Zhang1Wei Wang2Ji-Jun Gong3Zi-Jiang Liu4Hong-Shan Chen5State Key Laboratory of Advanced Processing and Recycling of Non-ferrous Metals, Lanzhou University of Technology, Lanzhou 730050, Gansu, ChinaState Key Laboratory of Advanced Processing and Recycling of Non-ferrous Metals, Lanzhou University of Technology, Lanzhou 730050, Gansu, ChinaDepartment of Applied Physics, Lanzhou University of Technology, Lanzhou 730050, Gansu, ChinaDepartment of Applied Physics, Lanzhou University of Technology, Lanzhou 730050, Gansu, ChinaDepartment of Physics, Lanzhou City University, Lanzhou 730070, Gansu, ChinaCollege of Physics and Electronic Engineering, Northwest Normal University, Lanzhou 730070, Gansu, ChinaThe understanding of the excited-state properties of electron donors, acceptors and their interfaces in organic optoelectronic devices is a fundamental issue for their performance optimization. In order to obtain a balanced description of the different excitation types for electron-donor-acceptor systems, including the singlet charge transfer (CT), local excitations, and triplet excited states, several ab initio and density functional theory (DFT) methods for excited-state calculations were evaluated based upon the selected model system of benzene-tetracyanoethylene (B-TCNE) complexes. On the basis of benchmark calculations of the equation-of-motion coupled-cluster with single and double excitations method, the arithmetic mean of the absolute errors and standard errors of the electronic excitation energies for the different computational methods suggest that the M11 functional in DFT is superior to the other tested DFT functionals, and time-dependent DFT (TDDFT) with the Tamm–Dancoff approximation improves the accuracy of the calculated excitation energies relative to that of the full TDDFT. The performance of the M11 functional underlines the importance of kinetic energy density, spin-density gradient, and range separation in the development of novel DFT functionals. According to the TDDFT results, the performances of the different TDDFT methods on the CT properties of the B-TCNE complexes were also analyzed.http://www.mdpi.com/1422-0067/19/4/1134excited statesab initiodensity functional theorydonor-acceptor complexescharge transfer |
| spellingShingle | Peng Xu Cai-Rong Zhang Wei Wang Ji-Jun Gong Zi-Jiang Liu Hong-Shan Chen Assessment of Ab Initio and Density Functional Theory Methods for the Excitations of Donor-Acceptor Complexes: The Case of the Benzene-Tetracyanoethylene Model International Journal of Molecular Sciences excited states ab initio density functional theory donor-acceptor complexes charge transfer |
| title | Assessment of Ab Initio and Density Functional Theory Methods for the Excitations of Donor-Acceptor Complexes: The Case of the Benzene-Tetracyanoethylene Model |
| title_full | Assessment of Ab Initio and Density Functional Theory Methods for the Excitations of Donor-Acceptor Complexes: The Case of the Benzene-Tetracyanoethylene Model |
| title_fullStr | Assessment of Ab Initio and Density Functional Theory Methods for the Excitations of Donor-Acceptor Complexes: The Case of the Benzene-Tetracyanoethylene Model |
| title_full_unstemmed | Assessment of Ab Initio and Density Functional Theory Methods for the Excitations of Donor-Acceptor Complexes: The Case of the Benzene-Tetracyanoethylene Model |
| title_short | Assessment of Ab Initio and Density Functional Theory Methods for the Excitations of Donor-Acceptor Complexes: The Case of the Benzene-Tetracyanoethylene Model |
| title_sort | assessment of ab initio and density functional theory methods for the excitations of donor acceptor complexes the case of the benzene tetracyanoethylene model |
| topic | excited states ab initio density functional theory donor-acceptor complexes charge transfer |
| url | http://www.mdpi.com/1422-0067/19/4/1134 |
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