Beyond Allen-Heine-Cardona: non-perturbative electron-phonon interactions in the linewidths and lineshifts of diamond

Abstract

The temperature-dependent band gap of solids is usually computed from the perturbative Allen-Heine-Cardona (AHC) electron-phonon self-energy evaluated on-shell. Extending AHC to arbitrary frequency $ω$ to determine the full spectral function via the Dyson equation is known to fail, misplacing satellites and yielding no broadening at band extrema, while non-perturbative supercell (SC) methods have focused on eigenvalue averages rather than lineshapes, and approaches based on special displacements cannot describe the full lineshape, or the lineshift at degenerate bands. Here we use a non-perturbative Green's function method (NPG), stochastically sampling distorted SC configurations, from which the spectral function, including lineshift, linewidth, and asymmetry, follows directly, and we recover finite spectral weight at the renormalized band extrema. We prove that the perturbative self-energy, computed to any order with the bare propagator and introduced into the Dyson equation, has an imaginary part that vanishes within the bare gap, giving incorrect spectral functions: self-consistency of the propagator is essential to broaden the band edges. NPG satisfies this property by construction, and contains all non-bubble diagrams. We also give a simple explanation of why SC methods converge with much smaller SCs than the corresponding $\mathbf{q}$-grids required by perturbation theory. For the band gap shift itself, the NPG and on-shell AHC results are found to be comparable, demonstrating that higher-order terms do not significantly alter the resulting renormalization in diamond. When it comes to the spectral function though, our results show that going beyond bare perturbation theory is not merely more accurate, but necessary, and NPG provides a robust framework to capture spectral broadening and higher-order effects from first principles.