Automated all-functionals infrared and Raman spectra

Abstract

Infrared and Raman spectroscopies are ubiquitous techniques employed in many experimental laboratories, thanks to their fast and non-destructive nature able to capture materials' features as spectroscopic fingerprints. Nevertheless, these measurements frequently need theoretical support in order to unambiguously decipher and assign complex spectra. Linear-response theory provides an effective way to obtain the higher-order derivatives needed, but its applicability to modern exchange-correlation functionals remains limited. Here, we devise an automated, open-source, user-friendly approach based on ground-state density-functional theory and the electric enthalpy functional to allow seamless calculations of first-principles infrared and Raman spectra. By employing a finite-displacement and finite-field approach, we allow for the use of any functional, as well as an efficient treatment of large low-symmetry structures. Additionally, we propose a simple scheme for efficiently sampling the Brillouin zone with different electric fields. To demonstrate the capabilities of our approach, we provide illustrations using the ferroelectric LiNbO${}_3$ crystal as a paradigmatic example. We predict infrared and Raman spectra using various (semi)local, Hubbard corrected, and hybrid functionals. Our results also show how PBE0 and extended Hubbard functionals yield in this case the best match in term of peak positions and intensities, respectively.

References in corpus (6)

• Quantum ESPRESSO: a modular and open-source software project for quantum simulations of materials
• Quantum ESPRESSO toward the exascale
• Self-consistent Hubbard parameters from density-functional perturbation theory in the ultrasoft and projector-augmented wave formulations
• Hubbard-corrected density functional perturbation theory with ultrasoft pseudopotentials
• Time-Dependent Self Consistent Harmonic Approximation: Anharmonic nuclear quantum dynamics and time correlation functions
• Automated all-functionals infrared and Raman spectra

Cited by in corpus (8)

• Automated all-functionals infrared and Raman spectra
• BaZrS${}_{\text{3}}$ Lights Up: The Interplay of Electrons, Photons, and Phonons in Strongly Luminescent Single Crystals
• First-principles Hubbard parameters with automated and reproducible workflows
• Automated computational workflows for muon spin spectroscopy
• Algorithmic differentiation for plane-wave DFT: materials design, error control and learning model parameters
• Ab initio functional-independent calculations of the clamped Pockels tensor of tetragonal barium titanate
• Making atomistic materials calculations accessible with the AiiDAlab Quantum ESPRESSO app
• Elastic Constants and Bending Rigidities from Long-Wavelength Perturbation Expansions