Paper published as part of the Quantum-Chemical Calculations and their applications special issue.
First-principles calculation of parameters of electron paramagnetic resonance spectroscopy in solids†
Article first published online: 5 SEP 2010
Copyright © 2010 John Wiley & Sons, Ltd.
Magnetic Resonance in Chemistry
Supplement: Quantum-Chemical Computations of Magnetic Resonance Parameters
Volume 48, Issue S1, pages S2–S10, December 2010
How to Cite
Kadantsev, E. S. and Ziegler, T. (2010), First-principles calculation of parameters of electron paramagnetic resonance spectroscopy in solids. Magn. Reson. Chem., 48: S2–S10. doi: 10.1002/mrc.2655
- Issue published online: 22 NOV 2010
- Article first published online: 5 SEP 2010
- Manuscript Accepted: 21 JUN 2010
- Manuscript Revised: 7 JUN 2010
- Manuscript Received: 31 MAR 2010
- ab initio;
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 S2 anion radical in KCl host crystal lattice. Copyright © 2010 John Wiley & Sons, Ltd.