All-Electron, Real-Space Perturbation Theory for Homogeneous Electric Fields: Theory, Implementation, and Application within DFT

Abstract

Within density-functional theory, perturbation theory~(PT) is the state-of-the-art formalism for assessing the response to homogeneous electric fields and the associated material properties, e.g., polarizabilities, dielectric constants, and Raman intensities. Here we derive a real-space formulation of PT and present an implementation within the all-electron, numeric atom-centered orbitals electronic structure code FHI-aims that allows for massively-parallel calculations. As demonstrated by extensive validation, this allows the rapid computation of accurate response properties of molecules and solids. As an application showcase, we present harmonic and anharmonic Raman spectra, the latter obtained by combining hundreds of thousands of PT calculations with \textit{ab initio} molecular dynamics. By using the PBE exchange-correlation functional with many-body van der Waals corrections, we obtain spectra in good agreement with experiment especially with respect to lineshapes for the isolated paracetamol molecule and two polymorphs of the paracetamol crystal.

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• First-Principles Simulations of Tip Enhanced Raman Scattering Reveal Active Role of Substrate on High-Resolution Images
• Predicting the Electronic Density Response of Condensed-Phase Systems to Electric Field Perturbations
• Efficient Parallel Linear Scaling Method to get the Response Density Matrix in All-Electron Real-Space Density-Functional Perturbation Theory
• Vibronic Couplings and Temperature Effects in the Ultrafast Dynamics of a Charge-Transfer Complex
• The Moving-Grid Effect in the Harmonic Vibrational Frequency Calculations with Numeric Atom-Centered Orbitals
• Phonon propagation scale and nanoscale order in vitreous silica from Raman spectroscopy
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• Learning the Electrostatic Response of the Electron Density through a Symmetry-Adapted Vector Field Model