期刊
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
卷 6, 期 21, 页码 4184-4188出版社
AMER CHEMICAL SOC
DOI: 10.1021/acs.jpclett.5b01888
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资金
- U.S. Department of Energy, Office of Basic Energy Sciences, through SciDAC [DE-SC0008666]
- Newman and Lillian Bortnick Fellowship in Chemistry at the University of Minnesota
- U.S. Department of Energy (DOE) [DE-SC0008666] Funding Source: U.S. Department of Energy (DOE)
Time-dependent Kohn-Sham density functional theory (TD-KS-DFT) is useful for calculating electronic excitation spectra of large systems, but the low-energy spectra are often complicated by artificially lowered higher-energy states. This affects even the lowest energy excited states. Here, by calculating the lowest energy spin-conserving excited state for atoms from H to K and for formaldehyde, we show that this problem does not occur in multiconfiguration pair-density functional theory (MC-PDFT). We use the tPBE on-top density functional, which is a translation of the PBE exchange-correlation functional. We compare to a robust multireference method, namely, complete active space second-order perturbation theory (CASPT2), and to TD-KS-DFT with two popular exchange-correlation functionals, PBE and PBE0. We find for atoms that the mean unsigned error (MUE) of MC-PDFT with the tPBE functional improves from 0.42 to 0.40 eV with a double set of diffuse functions, whereas the MUEs for PBE and PBE0 drastically increase from 0.74 to 2.49 eV and from 0.45 to 1.47 eV, respectively.
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