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First‐principles calculation of parameters of electron paramagnetic resonance spectroscopy in solids
Author(s) -
Kadantsev Eugene S.,
Ziegler Tom
Publication year - 2010
Publication title -
magnetic resonance in chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.483
H-Index - 72
eISSN - 1097-458X
pISSN - 0749-1581
DOI - 10.1002/mrc.2655
Subject(s) - electron paramagnetic resonance , chemistry , hyperfine structure , paramagnetism , tensor (intrinsic definition) , zeeman effect , atomic orbital , muonium , spin (aerodynamics) , basis set , atomic physics , electron , condensed matter physics , quantum mechanics , physics , density functional theory , magnetic field , computational chemistry , geometry , mathematics , thermodynamics
The hyperfine A ‐tensor and Zeeman g ‐tensor parameterize the interaction of an ‘effective’ electron spin with the magnetic field due to the nuclear spin and the homogeneous external magnetic field, respectively. The A ‐ and g ‐tensors are the quantities of primary interest in electron paramagnetic resonance (EPR) spectroscopy. In this paper, we review our work [E.S. Kadantsev, T. Ziegler, J. Phys. Chem. A 2008, 112, 4521; E. S. Kadantsev, T. Ziegler, J. Phys. Chem. A 2009, 113, 1327] on the calculation of these EPR parameters under periodic boundary conditions (PBC) from first‐principles. Our methodology is based on the Kohn‐Sham DFT (KS DFT), explicit usage of Bloch basis set made up of numerical and Slater‐type atomic orbitals (NAOs/STOs), and is implemented in the ‘full potential’ program BAND. Our implementation does not rely on the frozen core approximation. The NAOs/STOs basis is well suited for the accurate representation of the electron density near the nuclei, a prerequisite for the calculation of highly accurate hyperfine parameters. In the case of g ‐tensor, our implementation is based on the method of Van Lenthe et al. [E. van Lenthe, P. E. S. Wormer, A. van der Avoird, J. Chem. Phys. 1997, 107, 2488] in which the spin‐orbital coupling is taken into account variationally. We demonstrate the viability of our scheme by calculating EPR parameters of paramagnetic defects in solids. We consider the A ‐tensor of ‘normal’ and ‘anomalous’ muonium defect in IIIA‐VA semiconductors as well as the S 2 anion radical in KCl host crystal lattice. Copyright © 2010 John Wiley & Sons, Ltd.