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Is it worthwhile to go beyond the local‐density approximation in subsystem density functional theory?
Author(s) -
Grimmel Stephanie A.,
Teodoro Tiago Q.,
Visscher Lucas
Publication year - 2020
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.26111
Subject(s) - parametrization (atmospheric modeling) , density functional theory , context (archaeology) , kinetic energy , local density approximation , embedding , hybrid functional , time dependent density functional theory , statistical physics , excitation , orbital free density functional theory , yield (engineering) , computer science , physics , quantum mechanics , thermodynamics , artificial intelligence , paleontology , biology , radiative transfer
Frozen density embedding (FDE) theory is one of the major techniques aiming to bring modeling of extended chemical systems into the realm of high accuracy calculations. To improve its accuracy it is of interest to develop kinetic energy density functional approximations specifically for FDE applications. In the study reported here we focused on optimizing parameters of a generalized gradient approximation‐like kinetic energy functional with the purpose of better describing electron excitation energies. We found that our optimized parametrizations, named excPBE and excPBE‐3 (as these are derived from a Perdew‐Burke‐Ernzerhof‐like parametrization), could not yield improvements over available functionals when applied on a test set of systems designed to probe solvatochromic shifts. Moreover, as several different functionals yielded very similar errors to the simple local‐density approximation (LDA), it is questionable whether it is worthwhile to go beyond the LDA in this context.