Temperature-dependent vibrational EELS simulations with nuclear quantum effects

TL;DR

This paper introduces a novel simulation method combining TACAW and TRPMD to accurately model low-temperature vibrational EELS, capturing nuclear quantum effects and improving agreement with experimental observations.

Contribution

It develops an integrated framework that incorporates nuclear quantum effects into vibrational EELS simulations, enhancing accuracy at cryogenic temperatures.

Findings

Nuclear quantum effects significantly alter vibrational spectra at low temperatures.

The method predicts temperature-independent phonon peak intensities in silicon.

Results align with the first Born approximation for scattering intensities.

Abstract

The Time Autocorrelation of Auxiliary Wave (TACAW) method has established a framework for modeling angle-resolved electron energy loss spectroscopy (EELS) of phonons and magnons by deriving scattering intensities from the time autocorrelation of the beam wavefunction. This approach enables efficient computation of scattering intensities while naturally accounting for dynamical diffraction and multiple-scattering effects. In the cryogenic regime, vibrational spectra are dominated by nuclear quantum effects, notably zero-point motion. To capture these effects in low-temperature vibrational EELS, we incorporate thermostatted ring polymer molecular dynamics (TRPMD) into the TACAW formalism. Our results demonstrate that nuclear quantum effects lead to significant deviations from classical molecular dynamics predictions in the vibrational spectra of silicon at low temperatures and correctly predict the nearly temperature-independent optical phonon peak intensities in silicon, consistent with the first Born approximation. The TRPMD-TACAW method provides a robust theoretical tool for probing the low-temperature limit of vibrational EELS, offering a necessary benchmark for the quantitative analysis of emerging cryogenic scanning transmission electron microscopy experiments.