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

14 February 2022, Version 1
This content is a preprint and has not undergone peer review at the time of posting.


Time-dependent density functional theory has become state-of-the-art for describing photophysical and photochemical processes in extended materials due to 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 0.2 pm for excited-state bond lengths and in the range of 0.02 - 0.06 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 one order of magnitude can be achieved for ES geometry optimizations in comparison to conventional hybrid functionals. The second method is to use a semi-empirical 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 one order of magnitude, suggesting its potential use for large-scale screening purposes.


Theoretical spectroscopy
Excited-state properties
Exact exchange
Hybrid density functional theory
Tight binding

Supplementary materials

Supporting information for: Excited-state properties for extended systems: Efficient hybrid density functional methods
The supporting material comprises structural information on the molecular benchmark set, geometrical data on optimized molecular geometries, statistical analysis for vertical excitation, adiabatic excitation and fluorescence energies as well as structural information on covalent organic framework structures.


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