Co(iii) protoporphyrin IX chloride in solution: spin-state and metal coordination revealed from resonant inelastic X-ray scattering and electronic structure calculations
文献信息
Jie Xiao, Bernd Winter
The local electronic structure of the cobalt centre-ion of Co(III) protoporphyrin IX chloride dissolved in dimethyl sulfoxide (DMSO) liquid solution is studied by resonant inelastic X-ray scattering (RIXS) spectroscopy at the cobalt L-edge. The resulting cobalt 2p partial-fluorescence-yield (PFY) X-ray absorption (XA) spectrum, integrated from RIXS spectra, is simulated for various possible spin-states and coordination of the cobalt centre by using the newly developed density functional theory/restricted open shell single excitation configuration interaction (DFT/ROCIS) method. Comparison between experiment and calculation shows that the cobalt ion (3d6 electronic configuration) adopts a low-spin state with all six 3d electrons paired, and the cobalt centre is either 5-coordinated by its natural ligands (one chloride ion and four nitrogen atoms), or 6-coordinated, when binding to an oxygen atom of a DMSO solvent molecule. Analysis of the measured RIXS spectra reveals weak 3d–3d electron correlation, and in addition a value of the local HOMO–LUMO gap at the Co sites is obtained.
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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.













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