Calculation of magnetic properties with density functional approximations including rung 3.5 ingredients

Abstract

Density functional theory is widely used for modeling the magnetic properties of molecules, solids, and surfaces. Rung-3.5 ingredients, based on the expectation values of nonlocal one-electron operators, are new promising tools for the construction of exchange-correlation functional approximations. We present the formal extension of rung-3.5 ingredients to the calculation of magnetic properties. We add to the underlying nonlocal operators a dependence on the gauge of the magnetic field, and we derive the working equations for rung-3.5 expectation values in basis sets of gauge-including atomic orbitals. We demonstrate that the gauge corrections are significant. We conclude with an initial study of chemical shifts, optical rotatory dispersion, and Raman optical activity spectra predicted by M11plus, a range-separated hybrid meta functional incorporating nonlocal rung-3.5 correlation. M11plus proves to be reasonably accurate, further motivating the incorporation of nonlocal rung-3.5 ingredients in new density functional approximations.