The Electronic Structure of Permanganate Ion

Viste, Arlen; Gray, Harry B.

doi:10.1021/ic50018a011

Cited by 198 publications

(55 citation statements)

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“…17 The calculations also predict transitions that may account for the third low intensity and high-energy feature in the experimental spectra (see above). Consistent with our earlier report describing the NaReO 4 O K-edge spectrum, 21 and similar to several other ligand K-edge studies, 35,40-42 the electronic structure 8 calculations on MO 4 2-and MO 4 1-attribute this high-energy feature to transitions involving higher lying Rydberg-type orbitals.…”

Section: Resultsmentioning

confidence: 83%

“…21 Before presenting the experimental results, it is instructive to discuss the electronic structure calculations that guided spectral interpretations. Because the electronic structures for T d -MO 4 x-are well-established, 17,22 this discussion focuses on the unoccupied metal-based orbitals relevant to the O K-edge spectra (Figure 1). Results from the DFT calculations are consistent with group theory, and can be summarized as follows.…”

Section: Resultsmentioning

confidence: 99%

“…Overall, this provides two sets of unoccupied e* (π*; LUMO) and t 2 * (σ* + π*; LUMO+1) orbitals that primarily contain metal d character and is consistent with established bonding pictures for tetrahedral compounds. 17,[22][23][24] Density functional theory calculations using relativistic effective core potentials (RECPs) were conducted to determine how antibonding molecular orbital compositions and energies varied as (1) metals changed within a group (Cr, Mo, W and Mn, Tc, Re) and (2) metal charges increased from M 6+ (Group 6) to M 7+ (Group 7), which is accompanied by a decrease in anionic charge from MO 4 2-to MO 4 1-. The molecular orbital picture determined by DFT (Figure 1) is consistent with conclusions from group theory.…”

Section: Resultsmentioning

confidence: 99%

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Covalency in Metal–Oxygen Multiple Bonds Evaluated Using Oxygen K-edge Spectroscopy and Electronic Structure Theory

et al. 2013

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X-ray absorption spectroscopy using fluorescence and transmission (via a scanning transmission X-ray microscope), and linear-response density functional theory. The results suggest that moving from Group 6 to Group 7 or down the triads increases M-O e* (π*) mixing. Meanwhile, t 2 * mixing (σ* + π*) remains relatively constant within the same Group. These unexpected changes in frontier orbital energy and composition are evaluated in terms of periodic trends in d orbital energy and radial extension. 3Introduction.The nature of chemical bonds between metals and light atoms such as oxygen, nitrogen, and carbon is of widespread interest because these interactions control the physics and chemistry of many technologically important processes and compounds. Light atoms are prone to form highly covalent metalligand multiple bonds involving one σ bond and one or more π bonds, resulting in oxo, imido, nitrido, alkylidene, alkylidyne, and carbido functionalities with many desirable chemical reactivities and physical properties. 1 Among this diverse group, metal oxides stand out because of their widespread presence in biological and bio-inspired processes and for applications utilizing their unique magnetic, electronic, and thermal properties. [2][3][4][5][6][7][8][9][10][11][12][13] Developing a clear understanding of how M-O electronic structure and orbital mixing changes for a range of metal oxo compounds and materials will greatly benefit attempts to advance these technologies.Among approaches explored previously, ligand K-edge X-ray absorption spectroscopy (XAS) has emerged as an effective method for quantitatively probing electronic structure and orbital mixing in metal-chlorine and metal-sulfur bonds. 14 This spectroscopic technique probes bound state transitions between core ligand 1s orbitals and unoccupied molecular orbitals. The excitations can only have transition intensity if the empty acceptor orbitals contain ligand p character. 14 At first glance, such an approach seems well-suited for studying metal-oxygen bonding. However, attempts to use this technique to study non-conducting molecular systems are complicated by experimental barriers derived from the low energy of the oxygen K-edge (ca. 530 eV), which magnifies issues associated with surface contamination, saturation, and self-absorption effects.In this manuscript, we overcome these challenges and evaluate relative changes in metal-oxo electronic structure and orbital mixing for non-conducting molecular solids using O K-edge spectroscopy in conjunction with hybrid density functional theory (DFT) calculations. Specifically, non-resonant inelastic X-ray scattering (NIXS), XAS, and linear-response density functional theory (TDDFT) are used as Density functional theory calculations using relativistic effective core potentials (RECPs) were conducted to determine how antibonding molecular orbital compositions and energies varied as (1) metals 5 changed within a group (Cr, Mo, W and Mn, Tc, Re) and (2) metal charges increased from M 6+ (Group 6) to M 7+ (Group 7)...

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Section: Resultsmentioning

confidence: 83%

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

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Covalency in Metal–Oxygen Multiple Bonds Evaluated Using Oxygen K-edge Spectroscopy and Electronic Structure Theory

et al. 2013

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“…From the Racah parameters A 0 % 9442 cm À1 and B 0 % 1056 cm À1 of free Ni 2 ion [10], and the three observed transitions of NiO [2], we obtain N t % 0X8921, N e % 0X8923 and Dq % 890 cm À1 for NiO by using the above energy matrices. It can be seen that the difference between N t and N e is very small.…”

Section: For 3dmentioning

confidence: 98%

Investigations of the Pressure Dependence of Optical Spectra for NiO Crystal

Zheng

1999

phys. stat. sol. (a)

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The optical spectra and their pressure dependence for NiO crystal have been calculated by use of a modified crystal‐field theory, where the normalization parameters Nt and Ne describe the covalency reduction of electronic interactions for t2 and e orbitals and the pressure coefficients dNt/dP and dNe/dP are obtained from a cluster approach. The calculated results are in agreement with the observed values. The difficulty of the discrepancy in the change in Racah parameters B under pressure for the 3T1a and 3T1b transitions occurring in the conventional crystal‐field theory is removed.

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“…theory applied to transition metal compounds has been carried out for various ions and compounds (1)(2)(3)(4)(5)(6)(7)(8)(9)(10)(11)(12). Although the initial results are encouraging, it is clear that there is a need for a standard and consistent method of choosing the parameters in the calculation which can be transferred from one transition metal compound to another.…”

Section: Introductionmentioning

confidence: 99%

Extended Hückel molecular orbital calculations on some titanium–oxygen systems

Hsia¹

1968

Can. J. Chem.

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Extended Huckel molecular orbital calculations have been performed on localized TiOs8-units with the precise geometry of such a unit in solid rutile, anatase, and brookite TiO, and tetragonal BaTi03. The relative values of one-electron energy levels in these conlpounds are obtained in terms of a "self-consistent" charge and population calculation. Examination of the resulting energy levels and charge distributions has led to reasonable explanations of previously unexplained data on (1) the visible and near-ultraviolet absorption spectra of these compounds, (2) the low energy X-ray absorption edges of rutile, anatase, and brookite TiO,, and (3) the pressure dependence of the absorption edges of rutile TiO, and tetragonal BaTiO,.Canadian Journal of Chemistry, 46, 2667Chemistry, 46, (1968 IntroductionThe extended Hiickel molecular orbital (m.0.) theory applied to transition metal compounds has been carried out for various ions and compounds (1-12). Although the initial results are encouraging, it is clear that there is a need for a standard and consistent method of choosing the parameters in the calculation which can be transferred from one transition metal compound to another. It also seems desirable to explore whether this method can explain other phenomena besides the normal absorption spectra. Since the structures and optical data of rutile, anatase, and brookite TiO, and BaTiO, are available (13-26), it is of interest to examine these compounds by performing molecular orbital calculations on hypothetical localized Ti068-units with the exact geometries of the units in the parent compounds.

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The Electronic Structure of Permanganate Ion

Cited by 198 publications

References 3 publications

Covalency in Metal–Oxygen Multiple Bonds Evaluated Using Oxygen K-edge Spectroscopy and Electronic Structure Theory

Covalency in Metal–Oxygen Multiple Bonds Evaluated Using Oxygen K-edge Spectroscopy and Electronic Structure Theory

Investigations of the Pressure Dependence of Optical Spectra for NiO Crystal

Extended Hückel molecular orbital calculations on some titanium–oxygen systems

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