4.7 Article

Quadratic Response Properties from TDDFT: Trials and Tribulations

Journal

JOURNAL OF CHEMICAL THEORY AND COMPUTATION
Volume 14, Issue 2, Pages 807-819

Publisher

AMER CHEMICAL SOC
DOI: 10.1021/acs.jctc.7b01008

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Funding

  1. U.S. Department of Energy, Office of Basic Energy Sciences [DE-SC0018352]
  2. Arnold O. Beckman Postdoctoral Fellowship
  3. U.S. Department of Energy (DOE) [DE-SC0018352] Funding Source: U.S. Department of Energy (DOE)

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We report on the efficient TURBOMOLE implementation of quadratic response properties within the time-dependent density functional theory (TDDFT) context that includes the static and dynamic dipole hyperpolarizability, ground-to-excited-state two-photon absorption amplitudes (through a single residue) and state-to-state one-photon absorption amplitudes (through a double residue). Our implementation makes full use of arbitrary (including non-Abelian) point-group symmetry as well as permutational symmetry and enables the calculation of nonlinear properties with hybrid density functionals for molecules with hundreds of atoms and thousands of basis functions at a cost that is a fixed multiple of the cost of the corresponding linear properties. Using the PBE0 hybrid density functional, we show that excited-state absorption spectra computed within the pseudowavefunction approach contain the qualitative features of transient absorption spectra tracking excimer formation in perylene diimide dimers, two-photon absorption cross sections for a series of highly twisted fused porphyrin chains are semiquantitatively reproduced, and the computed dynamic hyperpolarizability of several calix[4]arene stereoisomers yield simulated hyper-Raleigh scattering signals consistent with experiment. In addition, we show that the incorrect pole structure of adiabatic TDDFT properties can cause incorrect excited-state absorption spectra and overly resonant hyperpolarizabilities, and discuss possible remedies.

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