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.
引用
收藏
页码:3284 / 3292
页数:9
相关论文
共 62 条
[1]   DIRECT, ATOMIC ORBITAL, STATIC EXCHANGE CALCULATIONS OF PHOTOABSORPTION SPECTRA OF LARGE MOLECULES AND CLUSTERS [J].
AGREN, H ;
CARRAVETTA, V ;
VAHTRAS, O ;
PETTERSSON, LGM .
CHEMICAL PHYSICS LETTERS, 1994, 222 (1-2) :75-81
[2]   Short-time Fourier transform analysis of real-time time-dependent Hartree-Fock and time-dependent density functional theory calculations with Gaussian basis functions [J].
Akama, Tomoko ;
Nakai, Hiromi .
JOURNAL OF CHEMICAL PHYSICS, 2010, 132 (05)
[3]   Understanding the Electronic Structure of 4d Metal Complexes: From Molecular Spinors to L-Edge Spectra of a di-Ru Catalyst [J].
Alperovich, Igor ;
Smolentsev, Grigory ;
Moonshiram, Dooshaye ;
Jurss, Jonah W. ;
Concepcion, Javier J. ;
Meyer, Thomas J. ;
Soldatov, Alexander ;
Pushkar, Yulia .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2011, 133 (39) :15786-15794
[4]   Structure and Hydrolysis of the U(IV), U(V), and U(VI) Aqua Ions from Ab Initio Molecular Simulations [J].
Atta-Fynn, Raymond ;
Johnson, Donald F. ;
Bylaska, Eric J. ;
Ilton, Eugene S. ;
Schenter, Gregory K. ;
de Jong, Wibe A. .
INORGANIC CHEMISTRY, 2012, 51 (05) :3016-3024
[5]   Real-time linear response for time-dependent density-functional theory [J].
Baer, R ;
Neuhauser, D .
JOURNAL OF CHEMICAL PHYSICS, 2004, 121 (20) :9803-9807
[6]   Treatment of electronic excitations within the adiabatic approximation of time dependent density functional theory [J].
Bauernschmitt, R ;
Ahlrichs, R .
CHEMICAL PHYSICS LETTERS, 1996, 256 (4-5) :454-464
[7]   Calculation of excitation energies within time-dependent density functional theory using auxiliary basis set expansions [J].
Bauernschmitt, R ;
Haser, M ;
Treutler, O ;
Ahlrichs, R .
CHEMICAL PHYSICS LETTERS, 1997, 264 (06) :573-578
[8]   A NEW MIXING OF HARTREE-FOCK AND LOCAL DENSITY-FUNCTIONAL THEORIES [J].
BECKE, AD .
JOURNAL OF CHEMICAL PHYSICS, 1993, 98 (02) :1372-1377
[9]   Time-dependent density functional theory calculations of the spectroscopy of core electrons [J].
Besley, Nicholas A. ;
Asmuruf, Frans A. .
PHYSICAL CHEMISTRY CHEMICAL PHYSICS, 2010, 12 (38) :12024-12039
[10]   Simulation of x-ray absorption near edge spectra of electronically excited ruthenium tris-2,2′-bipyridine [J].
Campbell, L ;
Mukamel, S .
JOURNAL OF CHEMICAL PHYSICS, 2004, 121 (24) :12323-12333