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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

(2011) JOURNAL OF PHYSICAL CHEMISTRY A. 115(9). p.1721-1733
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HPC-UGent: the central High Performance Computing infrastructure of Ghent University
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HPC-UGent: the central High Performance Computing infrastructure of Ghent University
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 Rh2+-related centers in NaCl. EPR experiments on NaCl:Rh single crystals identified three Rh2+ 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.
Keywords
SOLUTION-GROWN NACL, NUCLEAR DOUBLE-RESONANCE, DENSITY-FUNCTIONAL CALCULATIONS, ORDER REGULAR APPROXIMATION, INITIO MOLECULAR-DYNAMICS, ELECTRON-SPIN-RESONANCE, ALKALI-HALIDE LATTICES, MAGNETIC-RESONANCE, SINGLE-CRYSTALS, ATOMIC ORBITALS

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Chicago
Sakhabutdinova, Nuriya, Andy Van Yperen-De Deyne, Ewald Pauwels, Veronique Van Speybroeck, Henk Vrielinck, Freddy Callens, and Michel Waroquier. 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.” Journal of Physical Chemistry A 115 (9): 1721–1733.
APA
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. JOURNAL OF PHYSICAL CHEMISTRY A, 115(9), 1721–1733.
Vancouver
1.
Sakhabutdinova N, Van Yperen-De Deyne A, Pauwels E, Van Speybroeck V, Vrielinck H, Callens F, 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. JOURNAL OF PHYSICAL CHEMISTRY A. 2011;115(9):1721–33.
MLA
Sakhabutdinova, Nuriya, Andy Van Yperen-De Deyne, Ewald Pauwels, 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.” JOURNAL OF PHYSICAL CHEMISTRY A 115.9 (2011): 1721–1733. Print.
@article{1191997,
  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 Rh2+-related centers in NaCl. EPR experiments on NaCl:Rh single crystals identified three Rh2+ 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.},
  author       = {Sakhabutdinova, Nuriya and Van Yperen-De Deyne, Andy and Pauwels, Ewald and Van Speybroeck, Veronique and Vrielinck, Henk and Callens, Freddy and Waroquier, Michel},
  issn         = {1089-5639},
  journal      = {JOURNAL OF PHYSICAL CHEMISTRY A},
  keyword      = {SOLUTION-GROWN NACL,NUCLEAR DOUBLE-RESONANCE,DENSITY-FUNCTIONAL CALCULATIONS,ORDER REGULAR APPROXIMATION,INITIO MOLECULAR-DYNAMICS,ELECTRON-SPIN-RESONANCE,ALKALI-HALIDE LATTICES,MAGNETIC-RESONANCE,SINGLE-CRYSTALS,ATOMIC ORBITALS},
  language     = {eng},
  number       = {9},
  pages        = {1721--1733},
  title        = {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},
  url          = {http://dx.doi.org/10.1021/jp109517g},
  volume       = {115},
  year         = {2011},
}

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