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Updated: Jul 9, 2025

Excitonic Hamiltonians for Calculating Optical Absorption Spectra and Optoelectronic Properties of Molecular Aggregates and Solids
Published on: May 27, 2020
Oscillator strengths and excited-state couplings for double excitations in time-dependent density functional theory
Davood B Dar1, Neepa T Maitra1
1Department of Physics, Rutgers University, Newark, New Jersey 07102, USA.
Abstract:
Although useful to extract excitation energies of states of double-excitation character in time-dependent density functional theory that are missing in the adiabatic approximation, the frequency-dependent kernel derived earlier [Maitra et al., J. Chem. Phys. 120, 5932 (2004)] was not designed to yield oscillator strengths. These are required to fully determine linear absorption spectra, and they also impact excited-to-excited-state couplings that appear in dynamics simulations and other quadratic response properties. Here, we derive a modified non-adiabatic kernel that yields both accurate excitation energies and oscillator strengths for these states. We demonstrate its performance on a model two-electron system, the Be atom, and on excited-state transition dipoles in the LiH molecule at stretched bond-lengths, in all cases producing significant improvements over the traditional approximations.
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