Abstract
In 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.
Highlights
The fundamental energy gap or the band gap (BG) is an important intrinsic physical property of any solid material
As expected among all methods tested, the bt-pair natural orbital machinery (PNO)-STEOM-coupled cluster (CC) provides the best agreement with the available experimental values for singlet and triplet excitation energies as well as the fundamental energy gap
It was shown that combining the embedded cluster approach with bt-PNO-STEOM-CC, TD-density functional theory (DFT), or Δ-self-consistent field (SCF)/ DFT yields a computationally affordable computational protocol that is capable of computing a wide range of band gap energies (1.5−13.5 eV) of inorganic semiconductors
Summary
The fundamental energy gap or the band gap (BG) is an important intrinsic physical property of any solid material. It has been shown that exploiting the short-range character of the dynamical correlation in the framework of local correlation techniques can alter the severe limitations imposed by the steep scaling of the wave-function-based methods with system size and provide access to various surface problems.[40] In this direction, periodic local second-order Møller−Plesset perturbation theory (MP2) has been used to treat a number of surface problems.[21,22,41−44] for nonmetallic systems, it has been shown that embedded cluster models that treat the long-range electrostatics and polarization on a molecular mechanics level can lead to an effective reduction of the system size that needs to be treated quantum mechanically.[45−50] The combination of these two approaches has been proven instrumental for performing “gold standard” CCSD(T) level calculations for surface systems.[32,51] It has been shown that, provided that the quantum region is described at the level of the domain-based local pair natural orbital version of the CCSD(T) approach (DLPNO-CCSD(T)),[52] the adsorption energies for a set of small molecules at the rutile TiO2(110) surface can be computed with errors of
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