Quantitative prediction of optical absorption in molecular solids using an optimally tuned screened range-separated hybrid functional

ORAL

Abstract

Quantitative prediction of optical absorption in the solid-state using density functional theory (DFT) is a long-standing challenge. In principle, this should be possible with time-dependent DFT (TDDFT). In practice, the results depend very strongly on the approximate exchange-correlation functional and standard approximations usually fail qualitatively in the solid state. We show that such prediction is possible, using the recently-developed time-dependent optimally-tuned screenedrange-separated hybrid (OT-SRSH). In this method the molecular electronic structure is determined by optimal tuning of the range-separation parameter in a range-separated hybrid functional. Screening and polarization in the solid-state are taken into account by adding long-range dielectric screening to the functional form. We provide a comprehensive benchmark for the accuracy of this approach, by considering the X23 benchmark set of molecular solids. The results are in good agreement with many-body perturbation theory in the GW-BSE approximation. We discuss strengths and weaknesses of the approach. We believe that it could be used for studies of molecular solids typically outside the reach of computationally more intensive methods.

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Authors

  • Arun K. Manna

    • Weizmann Institute of Science

  • Sivan Refaely-Abramson

    • University of California
    • Molecular Foundry, Lawrence Berkeley National Lab; Dept. of Physics, University of California Berkeley, CA, USA

  • Anthony Reilly

    • The Cambridge Crystallographic Data Centre

  • Alexandre Tkatchenko

    • Physics and Materials Science Research Unit, University of Luxembourg, Luxembourg
    • University of Luxembourg

  • Jeffrey B. Neaton

    • Department of Physics, UC Berkeley; Molecular Foundry, LBNL
    • Department of Physics, UC Berkeley & Molecular Foundry, LBNL
    • Department of Physics, UC Berkeley; Molecular Foundry, LBNL; Kavli Energy NanoScience Institute
    • Department of Physics, University of California, Berkeley
    • Lawrence Berkeley National Laboratory
    • Molecular Foundry, LBNL; Dept. of Physics, UC Berkeley; Kavli ENSI
    • LBNL
    • Univ of California - Berkeley, Lawrence Berkeley National Lab
    • Physics, UC Berkeley, and Molecular Foundry, LBNL
    • University of California
    • Molecular Foundry, Lawrence Berkeley National Lab; Dept. of Physics, University of California Berkeley; Kavli NanoScience Institute, Berkeley, CA, USA
    • Department of Physics, UC Berkeley; Molecular Foundry, LBNL; Kavli Energy NanoSciences Institute at Berkeley
    • Physics Department, UC Berkeley; Molecular Foundry, Lawrence Berkeley National Lab; Kavli Energy NanoSciences Institute at Berkeley

  • Leeor Kronik

    • Weizmann Institute of Science, Rehovoth
    • Weizmann Institute of Science
    • Weizmann Institute of Science, Israel