Theory of X-ray absorption and emission spectra

Mukoyama, Takeshi

doi:10.1016/j.sab.2003.12.028

Cited by 11 publications

(7 citation statements)

References 52 publications

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“…X-ray emission spectra are simulated by computing the transition energy and the intensity, which is evaluated through the transition dipole moment. 100 The simplest approach to computing the intensity is to evaluate the transition dipole moment using the ground state orbitals, and this has been shown to give a surprisingly good agreement with experiment. 2,101 A physically more realistic approach is to use orbitals that account for the relaxation in the core-excited state.…”

Section: X-ray Emission Spectroscopymentioning

confidence: 99%

Time-dependent density functional theory calculations of the spectroscopy of core electrons

Besley

Asmuruf

2010

Phys. Chem. Chem. Phys.

244

380

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Recent advances in X-ray sources have led to a renaissance in spectroscopic techniques in the X-ray region. These techniques that involve the excitation of core electrons can provide an atom specific probe of electronic structure and provide powerful analytical tools that are used in many fields of research. Theoretical calculations can often play an important role in the analysis and interpretation of experimental spectra. In this perspective, we review recent developments in quantum chemical calculations of X-ray absorption spectra, focusing on the use of time-dependent density functional theory to study core excitations. The practical application of these calculations is illustrated with examples drawn from surface science and bioinorganic chemistry, and the application of these methods to study X-ray emission spectroscopy is explored.

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Section: X-ray Emission Spectroscopymentioning

confidence: 99%

Time-dependent density functional theory calculations of the spectroscopy of core electrons

Besley

Asmuruf

2010

Phys. Chem. Chem. Phys.

244

380

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“…This motivates the development of other methods, such as X-ray absorption spectroscopy (XAS). Considerable effort has gone into the application of XAS to Mn systems, as all oxidation states and spin states of Mn may be probed by X-ray core level spectroscopy. − For PSII, this has allowed for spectra of the S 0 to S 3 states of the Mn 4 Ca cluster to be obtained, thus providing significant insights into the oxidative transformations that occur in the cycle. − However, despite the advances reported in these studies, questions about the exact nature of some of the S states remain and there is a clear need for additional spectroscopic insights in order to fully assess changes in the electronic structure. In particular, a method that allows one to better assess changes in the ligand environment could provide key insights into our understanding of PSII and would also generally benefit our understanding of biological and chemical catalysis by Mn.…”

Section: Introductionmentioning

confidence: 99%

Manganese Kβ X-ray Emission Spectroscopy As a Probe of Metal–Ligand Interactions

et al. 2011

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A systematic series of high-spin mononuclear Mn(II), Mn(III), and Mn(IV) complexes has been investigated by manganese Kβ X-ray emission spectroscopy (XES). The factors contributing to the Kβ main line and the valence to core region are discussed. The Kβ main lines are dominated by 3p-3d exchange correlation (spin state) effects, shifting to lower energy upon oxidation of Mn(II) to Mn(III) due to the decrease in spin state from S = 5/2 to S = 2, whereas the valence to core region shows greater sensitivity to the chemical environment surrounding the Mn center. A density functional theory (DFT) approach has been used to calculate the valence to core spectra and assess the contributions to the energies and intensities. The valence spectra are dominated by manganese np to 1s electric dipole-allowed transitions and are particularly sensitive to spin state and ligand identity (reflected primarily in the transition energies) as well as oxidation state and metal-ligand bond lengths (reflected primarily in the transition intensities). The ability to use these methods to distinguish different ligand contributions within a heteroleptic coordination sphere is highlighted. The similarities and differences between the current Mn XES study and previous studies of Fe XES investigations are discussed. These findings serve as an important calibration for future applications to manganese active sites in biological and chemical catalysis.

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“…The hard X-ray probe ( h ν > 5 keV) has the advantage of very few restrictions with respect to the sample environment. A number of previous studies exist, − most notably perhaps the study of a series of Mn model systems with different ligands. , A quantitative interpretation of the Kβ satellites using density functional theory (DFT) proved the feasibility and potential of this approach …”

Section: Introductionmentioning

confidence: 99%

X-ray Emission Spectroscopy To Study Ligand Valence Orbitals in Mn Coordination Complexes

et al. 2009

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We discuss a spectroscopic method to determine the character of chemical bonding and for the identification of metal ligands in coordination and bioinorganic chemistry. It is based on the analysis of satellite lines in x-ray emission spectra that arise from transitions between valence orbitals and the metal ion 1s level (valence-to-core XES). The spectra, in connection with calculations based on density functional theory (DFT), provide information that is complementary to other spectroscopic techniques, in particular x-ray absorption (XANES and EXAFS). The spectral shape is sensitive to protonation of ligands and allows ligands, which differ only slightly in atomic number (e.g. C, N, O...), to be distinguished . A theoretical discussion of the main spectral features is presented in terms of molecular orbitals for a series of Mn model systems: [Mn(H2O)6]2+, [Mn(H2O)5OH]+, [Mn(H2O)5NH2]+ and [Mn(H2O)5NH3]2+. An application of the method, with comparison between theory and experiment, is presented for solvated Mn2+ ion in water and three Mn coordination complexes, namely [LMn(acac)N3]BPh4, [LMn(B2O3Ph2)(ClO4)] and [LMn(acac)N]BPh4 where L represents 1,4,7-trimethyl-1,4,7-triazacyclononane, acac stands for the 2,4-pentanedionate anion and B2O3Ph2 represents the 1,3-diphenyl-1,3-dibora-2-oxapropane-1,3-diolato dianion.

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Theory of X-ray absorption and emission spectra

Cited by 11 publications

References 52 publications

Time-dependent density functional theory calculations of the spectroscopy of core electrons

Time-dependent density functional theory calculations of the spectroscopy of core electrons

Manganese Kβ X-ray Emission Spectroscopy As a Probe of Metal–Ligand Interactions

X-ray Emission Spectroscopy To Study Ligand Valence Orbitals in Mn Coordination Complexes

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