Excitonic effects on the third-order nonlinear optical properties of solids: Theory and application

TL;DR

This paper develops a Bethe-Salpeter equation-based method to accurately compute the linear and nonlinear optical properties of solids, including excitonic effects, and applies it to C60 fullerene with results matching experiments.

Contribution

It introduces a sum-over-states approach incorporating excitonic and local field effects for nonlinear optical property calculations of solids.

Findings

Excitonic effects significantly alter spectral peak positions and intensities.

Theoretical spectra agree well with experimental data for C60.

Identifies nonlinear polarization resonances in third harmonic generation.

Abstract

We present a many-body Bethe-Salpeter equation eigenstates based sum-over-states method to calculate the linear and nonlinear optical properties of solids. Excitonic and local field effects are included in the calculations. As applications, we calculate the one-photon absorption, third harmonic generation, degenerate four-wave mixing spectra of solid C60 fullerene. The overall agreement between the theoretical and experimental results is very good for all three calculated spectra. By comparisons with the independent particle approximation based sum-over-states method, we show that excitonic effects mix the independent particle transition peaks to new excitonic ones. The position and intensity of spectral peaks are modified significantly. By tracing the sum-over-states progress, we determine the type of nonlinear polarization resonances for the characteristic peaks of third harmonic generation process, which may clear up a discrepancy in two experimental results.