Display options
Cite
Sakhabutdinova N, Van Yperen-De Deyne A, Pauwels E, et al. Assessment of periodic and cluster-in-vacuo models for first principles calculation of EPR parameters of paramagnetic defects in crystals: Rh2+ defects in NaCl as case study. J Phys Chem A. 2011;115(9):1721-33doi: 10.1021/jp109517g.
Sakhabutdinova, N., Van Yperen-De Deyne, A., Pauwels, E., Van Speybroeck, V., Vrielinck, H., Callens, F., & Waroquier, M. (2011). Assessment of periodic and cluster-in-vacuo models for first principles calculation of EPR parameters of paramagnetic defects in crystals: Rh2+ defects in NaCl as case study. The journal of physical chemistry. A, 115(9), 1721-33. https://doi.org/10.1021/jp109517g
Sakhabutdinova, N, et al. "Assessment of periodic and cluster-in-vacuo models for first principles calculation of EPR parameters of paramagnetic defects in crystals: Rh2+ defects in NaCl as case study." The journal of physical chemistry. A vol. 115,9 (2011): 1721-33. doi: https://doi.org/10.1021/jp109517g
Sakhabutdinova N, Van Yperen-De Deyne A, Pauwels E, Van Speybroeck V, Vrielinck H, Callens F, Waroquier M. Assessment of periodic and cluster-in-vacuo models for first principles calculation of EPR parameters of paramagnetic defects in crystals: Rh2+ defects in NaCl as case study. J Phys Chem A. 2011 Mar 10;115(9):1721-33. doi: 10.1021/jp109517g. Epub 2011 Feb 07. PMID: 21299236.
Copy Download .nbib Format: NLM
Share it on

J Phys Chem A. 2011 Mar 10;115(9):1721-33. doi: 10.1021/jp109517g. Epub 2011 Feb 07.

Assessment of periodic and cluster-in-vacuo models for first principles calculation of EPR parameters of paramagnetic defects in crystals: Rh2+ defects in NaCl as case study.

The journal of physical chemistry. A

N Sakhabutdinova, A Van Yperen-De Deyne, E Pauwels, V Van Speybroeck, H Vrielinck, F Callens, M Waroquier

Affiliations

  1. Center for Molecular Modeling, Ghent University, Zwijnaarde, Belgium.

PMID: 21299236 DOI: 10.1021/jp109517g

Abstract

In order to find a reliable and efficient calculation scheme for electron paramagnetic resonance (EPR) spectroscopic parameters for transition metal complexes in ionic solids from first principles, periodic and finite cluster-in-vacuo density functional theory (DFT) simulations are performed for g tensors, ligand hyperfine tensors (A), and quadrupole tensors (Q) for Rh(2+)-related centers in NaCl. EPR experiments on NaCl:Rh single crystals identified three Rh(2+) monomer centers, only differing in the number of charge compensating vacancies in their local environment, and one dimer center. Periodic and cluster calculations, both based on periodically optimized structures, are able to reproduce experimentally observed trends in the ligand A and Q tensors and render very satisfactory numerical agreement with experiment. Taking also computation time into account as a criterion, a full periodic approach emerges as most appropriate for these parameters.The g tensor calculations, on the other hand, prove to be insufficiently accurate for model assessment. The calculations also reveal parameters of the complexes which are not directly accessible through experiments, in particular related to their geometry.

Publication Types