Unveiling the Redox Noninnocence of Metallocorroles: Exploring K-Edge X-ray Absorption Near-Edge Spectroscopy with a Multiconfigurational Wave Function Approach

Khurana, Rishu; Liu, Cong

doi:10.1021/acs.jpclett.4c02410

Unveiling the Redox Noninnocence of Metallocorroles: Exploring K-Edge X-ray Absorption Near-Edge Spectroscopy with a Multiconfigurational Wave Function Approach

Journal Article · Fri Oct 25 00:00:00 EDT 2024 · Journal of Physical Chemistry Letters

DOI:https://doi.org/10.1021/acs.jpclett.4c02410· OSTI ID:2574985

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Univ. of Chicago, IL (United States); Argonne National Laboratory (ANL), Argonne, IL (United States)
Argonne National Laboratory (ANL), Argonne, IL (United States)

X-ray absorption near-edge spectroscopy (XANES) is an advanced technique for probing the local electronic structure of catalysts, effectively identifying the noninnocent nature of ligands in transition-metal complexes. Metallocorroles with noninnocent corrole rings exhibit unusual electronic structures that challenge traditional density functional theory (DFT) methods, necessitating more rigorous approaches to describe electron correlation accurately. We explored K-edge XANES spectra of Fe, Mn, and Co metallocorroles using TDDFT and wave function-based methods. This is the first investigation employing multireference methods, specifically RASSCF, RASPT2, and MC-PDFT, to analyze the redox noninnocent nature of metallocorroles reflected in their XANES spectra. We quantified the noninnocent character of the corrole and the oxidation states of the metals, capturing more than singly excited excitations responsible for the pre-edge peak. Our findings demonstrate the importance of these advanced computational techniques for accurately predicting XANES spectra, providing a reliable understanding of the electronic properties of such complexes. In conclusion, this study offers a new strategy for investigating ligand redox noninnocence via integrated experimental and computational XANES.

View Accepted Manuscript (DOE)

Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB); National Energy Research Scientific Computing Center (NERSC)

Grant/Contract Number:: SC0023382; AC02-06CH11357

OSTI ID:: 2574985

Journal Information:: Journal of Physical Chemistry Letters, Journal Name: Journal of Physical Chemistry Letters Journal Issue: 44 Vol. 15; ISSN 1948-7185

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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