Quadratic Response Properties from TDDFT: Trials and Tribulations.

J Chem Theory Comput

Department of Chemistry, University of California, Irvine , 1102 Natural Sciences II, Irvine, California 92697-2025, United States.

Published: February 2018

AI Article Synopsis

  • The text discusses a new, efficient implementation of quadratic response properties in time-dependent density functional theory (TDDFT), focusing on nonlinear optical properties and their calculations using hybrid density functionals.
  • It highlights the use of symmetries in calculations to handle large molecules with many atoms and basis functions, achieving efficient computations at a cost proportional to linear properties.
  • The findings suggest that their approach successfully reproduces experimental data related to excited-state absorption spectra and hyperpolarizabilities while addressing issues with incorrect results due to adiabatic TDDFT pole structures.

Article Abstract

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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http://dx.doi.org/10.1021/acs.jctc.7b01008DOI Listing

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