The Urbach tail in silica glass from first principles

TL;DR

This study uses first-principles density-functional theory to analyze the Urbach tail in silica glass, revealing exponential absorption edges, their relation to electronic states, and statistical properties of optical absorption near the edge.

Contribution

It establishes a direct link between absorption tails and electronic density-of-states, and characterizes the statistical nature of optical absorption in silica glass.

Findings

Exponential Urbach tails follow the Urbach rule in silica glass.

A relationship between absorption tails and electronic density-of-states is derived.

Optical absorption near the edge exhibits Poisson statistics with large fluctuations.

Abstract

We present density-functional theory calculations of the optical absorption spectra of silica glass for temperatures up to 2400 K. The calculated spectra exhibit exponential tails near the fundamental absorption edge that follow the Urbach rule, in good agreement with experiments. We also discuss the accuracy of our results by comparing to hybrid exchange correlation functionals. By deriving a simple relationship between the exponential tails of the absorption coefficient and the electronic density-of-states, we establish a direct link between the photoemission and the absorption spectra near the absorption edge. This relationship is subsequently employed to determine the lower bound to the Urbach frequency regime. Most interestingly, in this frequency interval, the optical absorption is Poisson distributed with very large statistical fluctuations. Finally, We determine the upper bound to the Urbach frequency regime by identifying the frequency at which transition to Poisson distribution takes place.