Excited-state properties for extended systems: Efficient hybrid density functional methods.

Hehn, Anna-Sophia, Sertcan, Beliz, Belleflamme, Fabian , Chulkov, Sergey, Watkins, Matthew and Hutter, Jürg (2022) Excited-state properties for extended systems: Efficient hybrid density functional methods. Journal of Chemical Theory and Computation, 18 (7). ISSN 1549-9618

Full content URL: https://doi.org/10.1021/acs.jctc.2c00144

Excited-state properties for extended systems: Efficient hybrid density functional methods.
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Time-dependent density functional theory has become state-of-the-art for describing photophysical and photochemical processes in extended materials because of its affordable cost. The inclusion of exact exchange was shown to be essential for the correct description of the long-range asymptotics of electronic interactions and thus a well-balanced description of valence, Rydberg, and charge-transfer excitations. Several approaches for an efficient treatment of exact exchange have been established for the ground state, while implementations for excited-state properties are rare. Furthermore, the high computational costs required for excited-state properties in comparison to ground-state computations often hinder large-scale applications on periodic systems with hybrid functional accuracy. We therefore propose two approximate schemes for improving computational efficiency for the treatment of exact exchange. Within the auxiliary density matrix method (ADMM), exact exchange is estimated using a relatively small auxiliary basis and the introduced basis set incompleteness error is compensated by an exchange density functional correction term. Benchmark results for a test set of 35 molecules demonstrate that the mean absolute error introduced by ADMM is smaller than 0.3 pm for excited-state bond lengths and in the range of 0.02–0.04 eV for vertical excitation, adiabatic excitation, and fluorescence energies. Computational timings for a series of covalent-organic frameworks demonstrate that a speed-up of at least 1 order of magnitude can be achieved for excited-state geometry optimizations in comparison to conventional hybrid functionals. The second method is to use a semiempirical tight binding approximation for both Coulomb and exchange contributions to the excited-state kernel. This simplified Tamm–Dancoff approximation (sTDA) achieves an accuracy comparable to approximated hybrid density functional theory when referring to highly accurate coupled-cluster reference data. We find that excited-state bond lengths deviate by 1.1 pm on average and mean absolute errors in vertical excitation, adiabatic excitation, and fluorescence energies are in the range of 0.2–0.5 eV. In comparison to ADMM-approximated hybrid functional theory, sTDA accelerates the computation of broad-band excitation spectra by 1 order of magnitude, suggesting its potential use for large-scale screening purposes.

Keywords:Theoretical spectroscopy, Excited-state properties, Exact exchange, Hybrid density functional theory, Tight binding
Subjects:F Physical Sciences > F200 Materials Science
F Physical Sciences > F343 Computational Physics
F Physical Sciences > F100 Chemistry
F Physical Sciences > F321 Solid state Physics
Divisions:College of Science > School of Mathematics and Physics
ID Code:50063
Deposited On:11 Jul 2022 09:38

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