Accounting all contributions for the Van Vleck paramagnetism and the Langevin diamagnetism from first principles: application to diamond

TL;DR

This paper presents a comprehensive first-principles method to calculate magnetic susceptibility in dielectrics, accounting for all contributions including Van Vleck and Langevin diamagnetism, and applies it successfully to diamond, demonstrating invariance and isotropy.

Contribution

The paper introduces a unified approach to compute magnetic susceptibility from first principles, including previously overlooked contributions, and applies it to diamond with detailed analysis.

Findings

Calculated magnetic susceptibility of diamond matches experimental data.

Demonstrated invariance of susceptibility sum under gauge transformations.

Showed isotropy of susceptibility in diamond across multiple directions.

Abstract

A general method for calculating magnetic susceptibility ($\chi$) in dielectrics within a single choice of magnetic gauge for the whole crystal is presented. On the basis of the method, accounting for all contributions to the Van Vleck paramagnetism and Langevin (Larmore) diamagnetism, a full-scale ab initio calculation of $\chi$ in diamond is performed. Unfamiliar contributions to $\chi$ includes a Van Vleck contribution from the interstitial region and an offset contribution from the muffin-tin (MT) sphere, appearing due to the change of the MT-sphere magnetic moment when the sphere is displaced from the origin. Although the Langevin diamagnetism explicitly depends on the choice of the origin, its sum with the Van Vleck term remains invariant, which is demonstrated on the basis of the gauge invariance of the magnetic vector potential. The derived expressions have been applied to ab initio calculations of magnetic susceptibility of the crystalline diamond within the linear augmented plane wave method (LAPW). With the diamond unit cell having the inversion symmetry, the magnetic (Van Vleck) calculations require the irreducible part of the Brillouin zone accounting for half of the whole zone, i.e. 24 times larger than that in the absence of magnetic field. Investigating possible anisotropy of $\chi$, we calculate it for 74 different directions of H (belonging to Lebedev surface grid points), and demonstrate that the actual value of $\chi$ remain isotropic. The obtained volume magnetic susceptibility in diamond lies in the range $16.27-16.72 (with the Langevin contribution -39.22-39.94 and the Van Vleck contribution -22.94-23.22), in units 10^{-7}, which compares well with the experimental data and other calculations.