TY - JOUR
T1 - All-electron, real-space perturbation theory for homogeneous electric fields
T2 - Theory, implementation, and application within DFT
AU - Shang, Honghui
AU - Raimbault, Nathaniel
AU - Rinke, Patrick
AU - Scheffler, Matthias
AU - Rossi, Mariana
AU - Carbogno, Christian
N1 - | openaire: EC/H2020/676580/EU//NoMaD
PY - 2018/7/1
Y1 - 2018/7/1
N2 - 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, we achieve a 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 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.
AB - 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, we achieve a 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 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.
KW - atom-centered basis functions
KW - coupled perturbed self-consistent field method
KW - density-functional perturbation theory
KW - homogeneous electric fields
KW - paracetamol
KW - Raman spectra
UR - http://www.scopus.com/inward/record.url?scp=85051105958&partnerID=8YFLogxK
U2 - 10.1088/1367-2630/aace6d
DO - 10.1088/1367-2630/aace6d
M3 - Article
AN - SCOPUS:85051105958
VL - 20
SP - 1
EP - 22
JO - New Journal of Physics
JF - New Journal of Physics
SN - 1367-2630
IS - 7
M1 - 073040
ER -