Spectroscopy of Transition‐Group Complexes

Jørgensen, Chr. Klixbüll

doi:10.1002/9780470143513.ch2

Cited by 191 publications

(30 citation statements)

References 240 publications

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“…Splitting of the second 4 T g state because of the ground state JT effect is experimentally not observed. 77 Possible spin-forbidden transitions are to the two 2 A g , two 2 E g , and four 2 T g excited states. Promotion of the two electrons from the t g orbitals to the e g orbitals gives the one 4 A g state, one 2 E g , and two 2 T g states.…”

Section: F Excitation Energies Of D 7 Complex Ion: [Co(h 2 O) 6 ] 2+mentioning

confidence: 99%

“…Second, whether the experimental assignation of the spectrum of [Fe(H 2 O) 6 ] 3+ is appropriate. 7,20,21 The series of TM aqua complexes was chosen due to the vast number of experimental [67][68][69][70][71][72][73][74][75][76][77][78][79][80][81][82][83] and computational results 7,20,49,[84][85][86][87][88][89][90] available for the assessment of the success of both the methods. In addition to the comparison of the results to the spectroscopic studies, [74][75][76][77][78][79][80][81][82][83] attention is payed to the comparison of our results to the recent high-level ab initio calculations by Neese et al 7 and Schatz et al 20 that were performed on the same series of molecules.…”

Section: Introductionmentioning

confidence: 99%

“…77 TD-DFT failed to reproduce experimental data for both [V(H 2 O) 6 ] 2+ and [Cr(H 2 O) 6 ] 3+ , Tables IV and V, in particular relative position of the first two bands. Furthermore, adiabatic TD-DFT is not able to calculate the experimentally observed77…”

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confidence: 99%

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Assessment of TD-DFT and LF-DFT for study of d − d transitions in first row transition metal hexaaqua complexes

Vlahović

Perić

Gruden

et al. 2015

The Journal of Chemical Physics

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Herein, we present the systematic, comparative computational study of the d - d transitions in a series of first row transition metal hexaaqua complexes, [M(H2O)6](n+) (M(2+/3+) = V (2+/3+), Cr(2+/3+), Mn(2+/3+), Fe(2+/3+), Co(2+/3+), Ni(2+)) by the means of Time-dependent Density Functional Theory (TD-DFT) and Ligand Field Density Functional Theory (LF-DFT). Influence of various exchange-correlation (XC) approximations have been studied, and results have been compared to the experimental transition energies, as well as, to the previous high-level ab initio calculations. TD-DFT gives satisfactory results in the cases of d(2), d(4), and low-spin d(6) complexes, but fails in the cases when transitions depend only on the ligand field splitting, and for states with strong character of double excitation. LF-DFT, as a non-empirical approach to the ligand field theory, takes into account in a balanced way both dynamic and non-dynamic correlation effects and hence accurately describes the multiplets of transition metal complexes, even in difficult cases such as sextet-quartet splitting in d(5) complexes. Use of the XC functionals designed for the accurate description of the spin-state splitting, e.g., OPBE, OPBE0, or SSB-D, is found to be crucial for proper prediction of the spin-forbidden excitations by LF-DFT. It is shown that LF-DFT is a valuable alternative to both TD-DFT and ab initio methods.

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Section: F Excitation Energies Of D 7 Complex Ion: [Co(h 2 O) 6 ] 2+mentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Assessment of TD-DFT and LF-DFT for study of d − d transitions in first row transition metal hexaaqua complexes

Vlahović

Perić

Gruden

et al. 2015

The Journal of Chemical Physics

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“…The starting point of crystal field multiplet theory is the approximation that the transition metal is an isolated ion with its electronic structure surrounded by a distribution of structure-less point charge sources, which mimic the symmetry around the central ion. Excellent textbooks on crystal field theory include Spectroscopy of Transition-Group Complexes [137] and Ligand Field Theory and the Properties of Transition Metal Complexes [186]. A recent review is Inorganic and Bioinorganic Spectroscopy [239].…”

Section: Theory B: Crystal Field Multiplet Theorymentioning

confidence: 99%

The iron L edges: Fe 2p X-ray absorption and electron energy loss spectroscopy

Miedema

Groot

2013

Journal of Electron Spectroscopy and Related Phenomena

132

106

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The iron L edges are reviewed. The experimental spectra obtained with 2p XAS, XMCD and 2p EELS are discussed, including isolated iron atoms, solids and coordination compounds. The largest fraction of publications deal with iron oxide systems that are discussed in detail, including binary oxides, perovskites and spinel systems. Emphasis is given on fundamental studies that focus on spectral shape analysis. We have selected a number of applications for further discussion, including iron in astrochemistry, iron complexes and nanostructures in catalysis, iron in mineralogy, the pnictide superconductors, spin crossover systems and phthalocyanine and related systems. Some of the important theoretical concepts in the analysis of L edges are discussed, including atomic multiplet theory, crystal field theory, charge transfer theory and XMCD. The 2p XAS spectra contain much detail for halides, oxides and coordination compounds. These spectra can be analyzed in great detail, revealing much information, including the valence, the spin state and the crystal field parameters. Covalent compounds and metal alloys have spectra with much less detail, which makes analysis more difficult.

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“…The starting point of crystal field multiplet theory is the approximation that the transition metal is an isolated ion with its electronic structure surrounded by a distribution of structure-less point charge sources, which mimic the symmetry around the central ion. Excellent textbooks on crystal field theory include Spectroscopy of Transition-Group Complexes [15] and Ligand Field Theory and the Properties of Transition Metal Complexes [16]. The effect of the cubic crystal field is that the seven 4f orbitals will lose their degeneracy and become split in energy into three distinct representations, respectively with T 1 , T 2 and A 2 symmetry.…”

Section: Detecting Crystal Field Effectsmentioning

confidence: 99%

Invisible structures in the X-ray absorption spectra of actinides

Kvashnina

Groot

2014

Journal of Electron Spectroscopy and Related Phenomena

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The X-ray absorption spectra of actinides are discussed with an emphasis on the fundamental effects that influence their spectral shape, including atomic multiplet theory, charge transfer theory and crystal field theory. Many actinide spectra consist of a single peak and it is shown that the use of resonant inelastic X-ray emission spectra (RIXS) has the potential to reveal many new features in the X-ray absorption spectra of actinides. The new range of RIXS beamlines will allow the determination of new structures in the X-ray absorption spectra that have been hitherto invisible. This has the potential to become an important tool in the determination of the electronic structure of actinides.

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Spectroscopy of Transition‐Group Complexes

Cited by 191 publications

References 240 publications

Assessment of TD-DFT and LF-DFT for study of d − d transitions in first row transition metal hexaaqua complexes

Assessment of TD-DFT and LF-DFT for study of d − d transitions in first row transition metal hexaaqua complexes

The iron L edges: Fe 2p X-ray absorption and electron energy loss spectroscopy

Invisible structures in the X-ray absorption spectra of actinides

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