Disentangling Transient Charge Density and Metal–Ligand Covalency in Photoexcited Ferricyanide with Femtosecond Resonant Inelastic Soft X-ray Scattering,The Journal of Physical Chemistry Letters

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Disentangling Transient Charge Density and Metal–Ligand Covalency in Photoexcited Ferricyanide with Femtosecond Resonant Inelastic Soft X-ray Scattering
The Journal of Physical Chemistry Letters ( IF 4.8 ) Pub Date : 2018-06-11 00:00:00 , DOI: 10.1021/acs.jpclett.8b01429
Raphael M. Jay ₁ , Jesper Norell ₂ , Sebastian Eckert _{1,

3} , Markus Hantschmann ₃ , Martin Beye _{3,

4} , Brian Kennedy ₃ , Wilson Quevedo ₃ , William F. Schlotter ₅ , Georgi L. Dakovski ₅ , Michael P. Minitti ₅ , Matthias C. Hoffmann ₅ , Ankush Mitra ₅ , Stefan P. Moeller ₅ , Dennis Nordlund ₆ , Wenkai Zhang ₆ , Huiyang W. Liang ₆ , Kristjan Kunnus ₆ , Katharina Kubiček ₄ , Simone A. Techert _{4,

7} , Marcus Lundberg _{8,

9} , Philippe Wernet ₃ , Kelly Gaffney ₆ , Michael Odelius ₂ , Alexander Föhlisch _{1,

3}

Affiliation

Soft X-ray spectroscopies are ideal probes of the local valence electronic structure of photocatalytically active metal sites. Here, we apply the selectivity of time-resolved resonant inelastic X-ray scattering at the iron L-edge to the transient charge distribution of an optically excited charge-transfer state in aqueous ferricyanide. Through comparison to steady-state spectra and quantum chemical calculations, the coupled effects of valence-shell closing and ligand-hole creation are experimentally and theoretically disentangled and described in terms of orbital occupancy, metal–ligand covalency, and ligand field splitting, thereby extending established steady-state concepts to the excited-state domain. π-Back-donation is found to be mainly determined by the metal site occupation, whereas the ligand hole instead influences σ-donation. Our results demonstrate how ultrafast resonant inelastic X-ray scattering can help characterize local charge distributions around catalytic metal centers in short-lived charge-transfer excited states, as a step toward future rationalization and tailoring of photocatalytic capabilities of transition-metal complexes.

中文翻译：

飞秒共振非弹性软X射线散射研究光激发铁氰化物中的瞬态电荷密度和金属配体价。

软X射线光谱学是光催化活性金属位点的局部价电子结构的理想探针。在这里，我们将在铁L边缘的时间分辨共振非弹性X射线散射的选择性应用于铁氰化物水溶液中光激发电荷转移态的瞬态电荷分布。通过比较稳态光谱和量子化学计算，从理论上解开了价壳关闭和配体孔形成的耦合效应，并根据轨道占有率，金属-配体价和配体场分裂来描述，从而扩展了建立稳态概念到激发态域。发现π-back-donation主要由金属位点占据决定，而配体孔反而影响σ-donation。

更新日期：2018-06-11

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