Comment on “State-Dependent Electron Delocalization Dynamics at the Solute-Solvent Interface: Soft-X-Ray Absorption Spectroscopy and Ab initio Calculations”

Green, R J; Peak, Derek; Achkar, Andrew; Tse, John S.; Moewes, A.; Hawthorn, D. G.; Regier, T. Z.

doi:10.1103/physrevlett.112.129301

Cited by 14 publications

(17 citation statements)

References 7 publications

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“…The role of delocalization and electron transfer processes in TFY and PFY detected x-ray absorption has recently been under debate [10][11][12][13][14][15] proving that speculations [16] severely overestimated charge delocalization based on the assignment of spectral features derived from x-ray optics [11,17] to charge transfer processes instead. Work on a selected model system with comprehensive experimental x-ray spectroscopic measurements, ab initio restricted active space self consisted field (RAS-SCF) for core-excited states in direct comparison to semi-empirical crystal field multiplet (CFM) has identified the statedependent fluorescence yield from the atomic dipole transition matrix elements as the crucial parameter to describe TFY and PFY in a rather localized atomic picture [17].…”

Section: Introductionmentioning

confidence: 99%

State-dependent fluorescence yields through the core-valence Coulomb exchange parameter

2014

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Total and partial fluorescence yield (PFY) L-edge x-ray absorption spectra differ from the transmission x-ray absorption spectra (XAS) through state-dependent fluorescence yield across the XAS. For 3d1 to 3d 9 in octahedral symmetry we apply simulations of PFY and XAS and show how the atomic 2p3d Coulomb exchange parameter G pd governs the differences in the L3/(L2+L3) branching ratio between PFY and XAS. G pd orders the XAS final states following Hund's rules creating a strong state-dependent fluorescence decay strength variation across the XAS leading to the differences between PFY and XAS.

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Section: Introductionmentioning

confidence: 99%

State-dependent fluorescence yields through the core-valence Coulomb exchange parameter

2014

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“…Using the more bulk sensitive fluorescence yield mode is not a viable alternative either, as it does not strictly represent absorption. 49,50 The best option whether RXR is not available is to terminate the sample with a protective layer. However, in many cases it will be difficult to find a material that does not itself change the film properties: it has to be lattice matched, of the same polarity, of comparable oxygen affinity and so on.…”

Section: Discussionmentioning

confidence: 99%

Valence-state reflectometry of complex oxide heterointerfaces

et al. 2016

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Emergent phenomena in transition-metal-oxide heterostructures such as interface superconductivity and magnetism have been attributed to electronic reconstruction, which, however, is difficult to detect and characterise. Here we overcome the associated difficulties to simultaneously address the electronic degrees of freedom and distinguish interface from bulk effects by implementing a novel approach to resonant X-ray reflectivity (RXR). Our RXR study of the chemical and valance profiles along the polar (001) direction of a LaCoO3 film on NdGaO3 reveals a pronounced valence-state reconstruction from Co3+ in the bulk to Co2+ at the surface, with an areal density close to 0.5 Co2+ ions per unit cell. An identical film capped with polar (001) LaAlO3 maintains the Co3+ valence over its entire thickness. We interpret this as evidence for electronic reconstruction in the uncapped film, involving the transfer of 0.5e -per unit cell to the subsurface CoO2 layer at its LaO-terminated polar surface

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“…47 Minor differences between the powder and aqueous spectra in our measurements could be attributed to state-dependent decay effects, which cause fluorescence yield measurements to deviate from absorption cross sections. 48 The character of transitions in ferri-and ferrocyanide was assigned based on ref. 40 .…”

Section: X-ray Absorption Of Ferri and Ferrocyanide Ions In The Flow mentioning

confidence: 99%

Reversibility of Ferri-/Ferrocyanide Redox during Operando Soft X-ray Spectroscopy

et al. 2015

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The ferri-ferrocyanide redox couple is ubiquitous in many fields of physical chemistry. We studied its photochemical response to intense synchrotron radiation by in-situ X-Ray absorption spectroscopy. For photon flux densities equal to and above 2×10 11 s -1 mm -2 , precipitation of ferric (hydr)oxide from both ferricyanide and ferrocyanide solutions was clearly detectable despite flowing fast enough to replace the solution in the flow cell every 0.4 s (flow rate 1.5 ml/min).During cyclic voltammetry, precipitation of ferric (hydr)oxide was promoted at reducing voltages and observed below 10 11 s -1 mm -2 . This was accompanied by inhibition of the ferriferrocyanide redox, which we probed by time-resolved operando X-ray absorption spectroscopy.Our study highlights the importance of considering both electrochemical and spectroscopic conditions when designing in-situ experiments.

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Comment on “State-Dependent Electron Delocalization Dynamics at the Solute-Solvent Interface: Soft-X-Ray Absorption Spectroscopy and Ab initio Calculations”

Cited by 14 publications

References 7 publications

State-dependent fluorescence yields through the core-valence Coulomb exchange parameter

State-dependent fluorescence yields through the core-valence Coulomb exchange parameter

Valence-state reflectometry of complex oxide heterointerfaces

Reversibility of Ferri-/Ferrocyanide Redox during Operando Soft X-ray Spectroscopy

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