Covalency Trends in Group IV Metallocene Dichlorides. Chlorine K-Edge X-Ray Absorption Spectroscopy and Time Dependent-Density Functional Theory

Kozimor, Stosh A.; Yang, Ping; Batista, Enrique R.; Boland, Kevin S.; Burns, Carol J.; Christensen, Christin N.; Clark, David L.; Conradson, Steven D.; Hay, P. Jeffrey; Lezama, Juan S.; Martin, Richard L.; Schwarz, Daniel E.; Wilkerson, Marianne P.; Wolfsberg, Laura E.

doi:10.1021/ic8004932

Cited by 47 publications

(81 citation statements)

References 56 publications

(153 reference statements)

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“…To evaluate the possible changes in Pd–P covalency in solution and the solid‐state, we performed dispersion‐corrected DFT and TDDFT calculations on 1 – 3 with a polarizable continuum model to simulate the CH 2 Cl 2 solution. The B3LYP functional was again selected because it has been shown to be remarkably accurate in the simulation of experimental XAS spectra via time‐dependent density functional theory (TDDFT) , , , , , , . For consistency, TDDFT calculations for 1 – 3 from our previous study were recalculated with dispersion corrections for comparison to the dispersion‐corrected solution calculations presented here.…”

Section: Resultsmentioning

confidence: 99%

Solution and Solid‐State Ligand K‐Edge XAS Studies of PdCl₂ Diphosphine Complexes with Phenyl and Cyclohexyl Substituents

et al. 2018

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Here we report P K-edge X-ray absorption spectroscopy (XAS), density functional theory (DFT), and time-dependent density functional theory (TDDFT) studies of [R 2 P(CH 2 ) n PR 2 ]PdCl 2 , where R = phenyl or cyclohexyl and n = 1-3. P K-edge XAS data were collected on room temperature CH 2 Cl 2 solutions of [Ph 2 P(CH 2 ) n PPh 2 ]PdCl 2 , where n = 1 (dppm; 1), 2 (dppe; 2), or 3 (dppp; 3) to determine if solid-state variations in covalent Pd-P bonding reported previously (Inorg. Chem. 2015, 54, 5646) were present in solution. A flow cell was used to overcome challenges associated with photon-induced decomposition, which often occurs rapidly in solution during ligand K-edge XAS data collection at room temperature. While [a]

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Section: Resultsmentioning

confidence: 99%

Solution and Solid‐State Ligand K‐Edge XAS Studies of PdCl₂ Diphosphine Complexes with Phenyl and Cyclohexyl Substituents

et al. 2018

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“…41,47,59,70,71,77,81-88 The computed spectra were carried out using linear response theory, based on density functional theory. This formalism is commonly referred in the community as TDDFT as it is from the time-dependent perturbation theory to DFT.…”

Section: Resultsmentioning

confidence: 99%

“…These calculations were conducted as previously described, 41,81-85,87,112 and involved evaluating core electron excitations by exploiting the small amount of mixing between the core orbitals and the high-lying unoccupied virtual orbitals. Specifically, this analysis involved a linear response calculation to extract the probability amplitudes from the transition densities and dipole moments between the calculated excited states and the ground states.…”

Section: Methodsmentioning

confidence: 99%

“…In fact, previous calculations on transition-metal compounds have provided very good agreement with experimental measurements. 41,81-85,87,112 For comparison with experiment, the first calculated TDDFT transition was shifted to match the maxima of the first experimental pre-edge peak, such that the MoS 4 2- and WS 4 2- TDDFT results were shifted by +56.6 eV and +56.7 eV, respectively. Because there was no experimental data for CrS 4 2- , the Cr TDDFT shift was determined by averaging the Mo and W values (+56.65 eV).…”

Section: Methodsmentioning

confidence: 99%

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Using solution- and solid-state S K-edge X-ray absorption spectroscopy with density functional theory to evaluate M–S bonding for MS₄²⁻(M = Cr, Mo, W) dianions

et al. 2014

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Herein, we have evaluated relative changes in M–S electronic structure and orbital mixing in Group 6 MS42- dianions using solid- and solution-phase S K-edge X-ray absorption spectroscopy (XAS; M = Mo, W), as well as density functional theory (DFT; M = Cr, Mo, W) and time-dependent density functional theory (TDDFT) calculations. To facilitate comparison with solution measurements (conducted in acetonitrile), theoretical models included gas-phase calculations as well as those that incorporated an acetonitrile dielectric, the latter of which provided better agreement with experiment. Two pre-edge features arising from S 1s → e* and t2* electron excitations were observed in the S K-edge XAS spectra and were reasonably assigned as 1A1 → 1T2 transitions. For MoS42-, both solution-phase pre-edge peak intensities were consistent with results from the solid-state spectra. For WS42-, solution- and solid-state pre-edge peak intensities for transitions involving e* were equivalent, while transitions involving the t2* orbitals were less intense in solution. Experimental and computational results have been presented in comparison to recent analyses of MO42- dianions, which allowed M–S and M–O orbital mixing to be evaluated as the principle quantum number (n) for the metal valence d orbitals increased (3d, 4d, 5d). Overall, the M–E (E = O, S) analyses revealed distinct trends in orbital mixing. For example, as the Group 6 triad was descended, e* (π*) orbital mixing remained constant in the M–S bonds, but increased appreciably for M–O interactions. For the t2* orbitals (σ* + π*), mixing decreased slightly for M–S bonding and increased only slightly for the M–O interactions. These results suggested that the metal and ligand valence orbital energies and radial extensions delicately influenced the orbital compositions for isoelectronic ME42- (E = O, S) dianions.

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“…Samples were prepared and NIXS and XAS experiments were performed as previously described, 29,[40][41][42] as were the calculations. 43…”

Section: Experimental and Calculation Methodsmentioning

confidence: 99%

Anomalous dispersion and band gap reduction in UO2+ and its possible coupling to the coherent polaronic quantum state

Conradson

Andersson

Bagus

et al. 2016

Nuclear Instruments and Methods in Physics Research Section B:

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Hypervalent UO 2 , UO 2(+x) formed by both addition of excess O and photoexcitation, exhibits a number of unusual or often unique properties that point to it hosting a polaronic Bose-Einstein(-Mott) condensate. A more thorough analysis of the O x-ray absorption spectra of UO 2 , U 4 O 9 , and U 3 O 7 shows that the anomalous increase in the width of the spectra features assigned to predominantly U 5f and 6d final states that points to increased dispersion of these bands occurs on the low energy side corresponding to the upper edge of the gap bordered by the conduction or upper Hubbard band. The closing of the gap by 1.5 eV is more than twice as much as predicted by calculations, consistent with the dynamical polaron found by structural measurements. In addition to fostering the excitation that is the proposed mechanism for the coherence, the likely mirroring of this effect on the occupied, valence side of the gap below the Fermi level points to increased complexity of the electronic structure that could be associated with the Fermi topology of BEC-BCS crossover and two band superconductivity.

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Covalency Trends in Group IV Metallocene Dichlorides. Chlorine K-Edge X-Ray Absorption Spectroscopy and Time Dependent-Density Functional Theory

Cited by 47 publications

References 56 publications

Solution and Solid‐State Ligand K‐Edge XAS Studies of PdCl₂ Diphosphine Complexes with Phenyl and Cyclohexyl Substituents

Solution and Solid‐State Ligand K‐Edge XAS Studies of PdCl₂ Diphosphine Complexes with Phenyl and Cyclohexyl Substituents

Using solution- and solid-state S K-edge X-ray absorption spectroscopy with density functional theory to evaluate M–S bonding for MS₄²⁻(M = Cr, Mo, W) dianions

Anomalous dispersion and band gap reduction in UO2+ and its possible coupling to the coherent polaronic quantum state

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Covalency Trends in Group IV Metallocene Dichlorides. Chlorine K-Edge X-Ray Absorption Spectroscopy and Time Dependent-Density Functional Theory

Cited by 47 publications

References 56 publications

Solution and Solid‐State Ligand K‐Edge XAS Studies of PdCl2 Diphosphine Complexes with Phenyl and Cyclohexyl Substituents

Solution and Solid‐State Ligand K‐Edge XAS Studies of PdCl2 Diphosphine Complexes with Phenyl and Cyclohexyl Substituents

Using solution- and solid-state S K-edge X-ray absorption spectroscopy with density functional theory to evaluate M–S bonding for MS42−(M = Cr, Mo, W) dianions

Anomalous dispersion and band gap reduction in UO2+ and its possible coupling to the coherent polaronic quantum state

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Solution and Solid‐State Ligand K‐Edge XAS Studies of PdCl₂ Diphosphine Complexes with Phenyl and Cyclohexyl Substituents

Solution and Solid‐State Ligand K‐Edge XAS Studies of PdCl₂ Diphosphine Complexes with Phenyl and Cyclohexyl Substituents

Using solution- and solid-state S K-edge X-ray absorption spectroscopy with density functional theory to evaluate M–S bonding for MS₄²⁻(M = Cr, Mo, W) dianions