ic9b00994_si_001.pdf (25.94 MB)
Accurate Band Gap Predictions of Semiconductors in the Framework of the Similarity Transformed Equation of Motion Coupled Cluster Theory
journal contribution
posted on 2019-06-26, 11:34 authored by Anneke Dittmer, Róbert Izsák, Frank Neese, Dimitrios MaganasIn
this work, we present a detailed comparison between wave-function-based
and particle/hole techniques for the prediction of band gap energies
of semiconductors. We focus on the comparison of the back-transformed
Pair Natural Orbital Similarity Transformed Equation of Motion Coupled-Cluster
(bt-PNO-STEOM-CCSD) method with Time Dependent Density Functional
Theory (TD-DFT) and Delta Self Consistent Field/DFT (Δ-SCF/DFT)
that are employed to calculate the band gap energies in a test set
of organic and inorganic semiconductors. Throughout, we have used
cluster models for the calculations that were calibrated by comparing
the results of the cluster calculations to periodic DFT calculations
with the same functional. These calibrations were run with cluster
models of increasing size until the results agreed closely with the
periodic calculation. It is demonstrated that bt-PNO-STEOM-CC yields
accurate results that are in better than 0.2 eV agreement with the
experiment. This holds for both organic and inorganic semiconductors.
The efficiency of the employed computational protocols is thoroughly
discussed. Overall, we believe that this study is an important contribution
that can aid future developments and applications of excited state
coupled cluster methods in the field of solid-state chemistry and
heterogeneous catalysis.