Strong anisotropic influence of local-field effects on the dielectric response of {\alpha}-MoO3

TL;DR

This study combines experimental and ab initio methods to reveal that local-field effects critically influence the anisotropic dielectric response of {eta}-MoO3, especially affecting spectral features and electron density distribution.

Contribution

It demonstrates the essential role of local-field effects in accurately modeling the dielectric properties and anisotropy of {eta}-MoO3, linking electron density inhomogeneity to spectral behavior.

Findings

LFE are crucial for accurate spectral predictions.

Strong anisotropy in dielectric response driven by LFE.

Inhomogeneous electron density around terminal oxygens affects LFE influence.

Abstract

Dielectric properties of {\alpha}-MoO3 are investigated by a combination of valence electron-energy loss spectroscopy and ab initio calculation at the random phase approximation level with the inclusion of local-field effects (LFE). A meticulous comparison between experimental and calculated spectra is performed in order to interpret calculated dielectric properties. The dielectric function of MoO3 has been obtained along the three axes and the importance of LFE has been shown. In particular, taking into account LFE is shown to be essential to describe properly the intensity and position of the Mo-N2,3 edges as well as the low energy part of the spectrum. A detailed study of the energy-loss function in connection with the dielectric response function also shows that the strong anisotropy of the energy-loss function of {\alpha}-MoO3 is driven by an anisotropic influence of LFE. These LFE significantly dampen a large peak in {\epsilon}2, but only along the [010] direction. Thanks to a detailed analysis at specific k-points of the orbitals involved in this transition, the origin of this peak has not only been evidenced but a connection between the inhomogeneity of the electron density and the anisotropic influence of local-field effects has also been established. More specifically, this anisotropy is governed by a strongly inhomogeneous spatial distribution of the empty states. This depletion of the empty states is localized around the terminal oxygens and accentuates the electron inhomogeneity.