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

wim — Mon, 22 Aug 2011 14:36:20 +0000

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

Journal of Physical Chemistry A

115(9), 1721-1733

2011

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.

DOI

http://dx.doi.org/10.1021/jp109517g

DFT characterisation of structural and EPR properties of Rh defects in alkali halide lattices

wim — Mon, 17 Oct 2011 14:33:54 +0000

N. Sakhabutdinova, E. Pauwels, H. Vrielinck, F. Callens, M. Waroquier

Poster

Conference / event / venue

7th European Federation of EPR (EFEPR) Groups Meeting and Closing Meeting of COST P15

Antwerp, Belgium

Sunday, 6 September, 2009 to Friday, 11 September, 2009

DFT characterisation of structural and EPR properties of Rh defects in alkali halide lattices

wim — Mon, 17 Oct 2011 14:27:42 +0000

N. Sakhabutdinova, E. Pauwels, H. Vrielinck, F. Callens, M. Waroquier

Poster

Conference / event / venue

Comp.Chemistry Summer School

Essen, Germany

Tuesday, 22 September, 2009 to Friday, 25 September, 2009

Nuriya Sakhabutdinova

wim — Tue, 23 Aug 2011 13:43:45 +0000

Center for Molecular Modeling - N. Sakhabutdinova

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

Abstract

DOI

DFT characterisation of structural and EPR properties of Rh defects in alkali halide lattices

Conference / event / venue

DFT characterisation of structural and EPR properties of Rh defects in alkali halide lattices

Conference / event / venue

Nuriya Sakhabutdinova