Magnetic exchange couplings from noncollinear spin density functional perturbation theory

2008/10/15 by Juan E. Peralta, Veronica Barone, Verónica Barone
Chemistry · Materials Science · Physics and Astronomy · #Advanced Condensed Matter Physics #Advanced NMR Techniques and Applications #Magnetism in coordination complexes #cond-mat.mtrl-sci #cond-mat.other

paper · pdf · doi:10.1063/1.3013602

J.Chem. Phys. (accepted)

arxiv created 2008/10/15 · openalex publication_date 2008/11/19 · arxiv updated 2009/12/01 · openalex created_date 2025/10/10 · openalex updated_date 2026/07/28

Abstract

We propose a method for the evaluation of magnetic exchange couplings based on noncollinear spin density functional calculations. The method employs the second derivative of the total Kohn-Sham energy of a single reference state, in contrast to approximations based on Kohn-Sham total energy differences. The advantage of our approach is twofold: It provides a physically motivated picture of the transition from a low-spin to a high-spin state, and it utilizes a perturbation scheme for the evaluation of magnetic exchange couplings. The latter simplifies the way these parameters are predicted using first principles: It avoids the nontrivial search for different spin states that needs to be carried out in energy difference methods, and it opens the possibility of "black-boxifying" the extraction of exchange couplings from density functional theory calculations. We present proof of concept calculations of magnetic exchange couplings in the H-He-H model system and in an oxovanadium bimetallic complex where the results can be intuitively rationalized.

Citations

• Noncollinear magnetism in density functional calculations
• A local exchange-correlation potential for the spin polarized case. i
• On the parameterization of the local correlation functional. What is Becke-3-LYP?
• Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density
• Accurate spin-dependent electron liquid correlation energies for local spin density calculations: a critical analysis
• Fully optimized contracted Gaussian basis sets of triple zeta valence quality for atoms Li to Kr
• Fully optimized contracted Gaussian basis sets for atoms Li to Kr
• On the Non-Orthogonality Problem Connected with the Use of Atomic Wave Functions in the Theory of Molecules and Crystals
• Density-functional thermochemistry. III. The role of exact exchange
• Ab Initio Calculation of Vibrational Absorption and Circular Dichroism Spectra Using Density Functional Force Fields
• Self-Consistent Equations Including Exchange and Correlation Effects