Theory of the charge response of the boron-vacancy spin in monolayer hexagonal boron nitride

Abstract

The boron vacancy $V_{\mathrm{B}}^{-}$ in hexagonal boron nitride is a leading two-dimensional spin sensor, but the microscopic connection between nearby charge positions and its spin Hamiltonian remains poorly understood. Calculations for carbon and oxygen donors 3.85--8.08 $\mathring{\mathrm{A}}$ away show that direction matters, not only distance. In the frozen lattice, reversing a carbon donor's azimuth at 4.35 $\mathring{\mathrm{A}}$ (C1 to C1m) more than halves $|E|$ and turns its axis across the mirror line. The ratio is 0.467 with the Perdew--Burke--Ernzerhof (PBE) functional, against 1 for distance alone. A field-plus-gradient model fitted to six donor configurations, including C1 but excluding C1m, predicted a ratio of 0.443 before C1m was calculated. Heyd--Scuseria--Ernzerhof hybrid statics give 0.432 and PBE relaxation 0.600. Exploratory analysis suggests why direction matters: a charge's potential differs at the three vacancy nitrogens and moves the spin of the two $e'$ holes among them, more when the charge faces one nitrogen than the gap between two. $E$ follows this spin imbalance through one constant, $c\approx8$ GHz per $μ_{\mathrm{B}}$, across donors and applied fields, whereas in PBE $D$ is nearly insensitive to it. A three-site model with one fitted screening constant reproduces the frozen-lattice $E$ to 83 MHz rms. Results are for one charge state in a free-standing monolayer; absolute $|E|$ varies by tens of percent across approximations.