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Linear-Response and Real-Time Time-Dependent Density Functional Theory Studies of Core-Level Near-Edge X-Ray Absorption
被引:207
作者:
Lopata, K.
[1
]
Van Kuiken, B. E.
[2
]
Khalil, M.
[2
]
Govind, N.
[1
]
机构:
[1] Pacific NW Natl Lab, William R Wiley Environm Mol Sci Lab, Richland, WA 99352 USA
[2] Univ Washington, Dept Chem, Seattle, WA 98195 USA
关键词:
ELECTRONIC-STRUCTURE;
HARTREE-FOCK;
INNER-SHELL;
BASIS-SET;
SPECTRA;
MOLECULES;
SPECTROSCOPY;
APPROXIMATION;
EXCITATIONS;
ENERGIES;
D O I:
10.1021/ct3005613
中图分类号:
O64 [物理化学(理论化学)、化学物理学];
学科分类号:
070304 ;
081704 ;
摘要:
We discuss our implementation and application of time-dependent density functional theory (TDDFT) to core-level near-edge absorption spectroscopy, using both linear-response (LR) and real-time (RT) approaches. We briefly describe our restricted excitation window TDDFT (REW-TDDFT) approach for core excitations, which has also been reported by other groups. This is followed by a detailed discussion of real-time TDDFT techniques tailored to core excitations, including obtaining spectral information through delta-function excitation, postprocessing time-dependent signals, and resonant excitation through quasi-monochromatic excitation. We present results for the oxygen K-edge of water and carbon monoxide; the carbon K-edge of carbon monoxide; the ruthenium L-3-edge for the hexaamminerutheium(III) ion, including scalar relativistic corrections via the zeroth order regular approximation (ZORA); and the carbon and fluorine K-edges for a series of fluorobenzenes. In all cases, the calculated spectra are found to be in reasonable agreement with experimental results, requiring only a uniform shift ranging from -4 eV to +19 eV, i.e., on the order of a few percent of the excitation energy. Real-time TDDFT visualization of excited state charge densities is used to visually examine the nature of each excitation, which gives insight into the effects of atoms bound to the absorbing center.
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页码:3284 / 3292
页数:9
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