Analytical nuclear excited-state gradients for the Tamm–Dancoff approximation using uncoupled frozen-density embedding

5 years ago

Analytical nuclear excited-state gradients for the Tamm–Dancoff approximation using uncoupled frozen-density embedding

Sebastian Höfener, Johannes Heuser

We report the derivation and implementation of analytical nuclear gradients for excited states using time-dependent density functional theory using the Tamm–Dancoff approximation combined with uncoupled frozen-density embedding using density fitting. Explicit equations are presented and discussed. The implementation is able to treat singlet as well as triplet states and functionals using the local density approximation, the generalized gradient approximation, combinations with Hartree–Fock exchange (hybrids), and range-separated functionals such as CAM-B3LYP. The new method is benchmarked against supermolecule calculations in two case studies: The solvatochromic shift of the (vertical) fluorescence energy of 4-aminophthalimide on solvation, and the first local excitation of the benzonitrile dimer. Whereas for the 4-aminophthalimide–water complex deviations of about 0.2 eV are obtained to supermolecular calculations, for the benzonitrile dimer the maximum error for adiabatic excitation energies is below 0.01 eV due to a weak coupling of the subsystems. © 2017 Wiley Periodicals, Inc. We report analytical nuclear excited-state Tamm–Dancoff gradients for uncoupled frozen-density embedding (FDEu) using density fitting. For the benzonitrile dimer, the deviations to a supermolecular geometry optimization result in an error below 0.01 eV for the adiabatic transition energy.

Publisher URL: http://onlinelibrary.wiley.com/resolve/doi

DOI: 10.1002/jcc.24885