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Seeing colors with TDDFT: theoretical modeling of the optical properties of natural dyes

Ge, Xiaochuan
2013-11-18
  • doctoral thesis

Abstract
We have presented a newly developed Davidson-like algorithm to compute selected \textit{interior} eigenstates of the Liouvillian super-operator, and a recently introduced \textit{pseudo-Hermitian} variant of the Liouville-Lanczos approach to time-dependent density-functional theory (TDDFT). The new algorithms have been released as the new version of \texttt{turboTDDFT} in the \textsc{Quantum ESPRESSO} package together with an implementation of hybrid functionals. Our implementation has been thoroughly validated against benchmark calculations performed on a few moleucles using both the original \texttt{turboTDDFT} and \texttt{Gaussian09} code. Then we have applied the new algorithms to carry on a systematic study of anthocyanins' optical properties. We have found that the Oxygen-containing side groups on the phenyl ring of these molecules play important roles to modify their optical absorption spectra, which can be understood by a so-call \textit{double-pole approximation}. We have also applied a recently proposed explicit solvent model to study the solvent effects for these molecules, using a combination of Ab-initio molecular dynamics (AIMD) and TDDFT. We have found that PBE produces too red-shifted spectra, instead B3LYP gives the spectra and the simulated colors in very good agreement with the experiment.
Archivio
http://hdl.handle.net/20.500.11767/4816
Diritti
open access
Soggetti
  • time-dependent densit...

  • davidson-like algorit...

  • truboTDDFT

  • pseudo-Hermitian Lanc...

  • hybrid functional

  • anthocyanin

  • explicit solvent mode...

  • double-pole approxima...

  • optical spectrum

Visualizzazioni
1
Data di acquisizione
Apr 19, 2024
Vedi dettagli
google-scholar
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