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Title: Ab Initio Analysis of Metal–Ligand Bonding in An(COT) 2 with An=Th, U in Their Ground‐ and Core‐Excited States

Abstract

Abstract Relativistic multireference ab initio wave function calculations with the restricted active space second‐order perturbation theory (RASPT2) were performed on thorocene and uranocene to determine the actinide N 4,5 ‐edge and carbon K‐edge X‐ray absorption near‐edge structure (XANES) intensities and the metal–ligand orbital mixing in the ground state and core‐excited states. Calculated spectral intensities show very good agreement with the experiments and therefore allow detailed and unambiguous assignment of the observed spectral features. φ ‐type covalent bonding or antibonding interactions are observed for thorocene in the core‐excited states, though not in the ground state. This is because the molecular orbital of φ symmetry, which is the in‐phase combination of the ligand L φ and the Th 5f φ orbitals, can be populated with electrons in core‐excited states, whereas it is essentially unoccupied in the ground state. For uranocene, the XANES spectra do not reveal much information beyond multiplet broadening, despite the presence of distinct peaks in the spectra. Every core‐excited peak is best characterized by its own set of bond orbitals, as the excited state covalency is clearly different from the ground state covalency.

Authors:
ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]
  1. Department of Chemistry University at Buffalo State University of New York Buffalo NY 14260-3000 USA
Publication Date:
Sponsoring Org.:
USDOE
OSTI Identifier:
1582477
Grant/Contract Number:  
SC0001136
Resource Type:
Publisher's Accepted Manuscript
Journal Name:
Chemistry - A European Journal
Additional Journal Information:
Journal Name: Chemistry - A European Journal Journal Volume: 26 Journal Issue: 8; Journal ID: ISSN 0947-6539
Publisher:
Wiley Blackwell (John Wiley & Sons)
Country of Publication:
Germany
Language:
English

Citation Formats

Ganguly, Gaurab, Sergentu, Dumitru‐Claudiu, and Autschbach, Jochen. Ab Initio Analysis of Metal–Ligand Bonding in An(COT) 2 with An=Th, U in Their Ground‐ and Core‐Excited States. Germany: N. p., 2020. Web. doi:10.1002/chem.201904166.
Ganguly, Gaurab, Sergentu, Dumitru‐Claudiu, & Autschbach, Jochen. Ab Initio Analysis of Metal–Ligand Bonding in An(COT) 2 with An=Th, U in Their Ground‐ and Core‐Excited States. Germany. https://doi.org/10.1002/chem.201904166
Ganguly, Gaurab, Sergentu, Dumitru‐Claudiu, and Autschbach, Jochen. Mon . "Ab Initio Analysis of Metal–Ligand Bonding in An(COT) 2 with An=Th, U in Their Ground‐ and Core‐Excited States". Germany. https://doi.org/10.1002/chem.201904166.
@article{osti_1582477,
title = {Ab Initio Analysis of Metal–Ligand Bonding in An(COT) 2 with An=Th, U in Their Ground‐ and Core‐Excited States},
author = {Ganguly, Gaurab and Sergentu, Dumitru‐Claudiu and Autschbach, Jochen},
abstractNote = {Abstract Relativistic multireference ab initio wave function calculations with the restricted active space second‐order perturbation theory (RASPT2) were performed on thorocene and uranocene to determine the actinide N 4,5 ‐edge and carbon K‐edge X‐ray absorption near‐edge structure (XANES) intensities and the metal–ligand orbital mixing in the ground state and core‐excited states. Calculated spectral intensities show very good agreement with the experiments and therefore allow detailed and unambiguous assignment of the observed spectral features. φ ‐type covalent bonding or antibonding interactions are observed for thorocene in the core‐excited states, though not in the ground state. This is because the molecular orbital of φ symmetry, which is the in‐phase combination of the ligand L φ and the Th 5f φ orbitals, can be populated with electrons in core‐excited states, whereas it is essentially unoccupied in the ground state. For uranocene, the XANES spectra do not reveal much information beyond multiplet broadening, despite the presence of distinct peaks in the spectra. Every core‐excited peak is best characterized by its own set of bond orbitals, as the excited state covalency is clearly different from the ground state covalency.},
doi = {10.1002/chem.201904166},
journal = {Chemistry - A European Journal},
number = 8,
volume = 26,
place = {Germany},
year = {2020},
month = {1}
}

Journal Article:
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https://doi.org/10.1002/chem.201904166

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