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Updated: Mar 29, 2026
Excitonic Hamiltonians for Calculating Optical Absorption Spectra and Optoelectronic Properties of Molecular Aggregates and Solids
Published on: May 27, 2020
Predictions of Optical Excitations in Transition-Metal Complexes with Time Dependent-Density Functional Theory:
Laurence Petit1, Pascale Maldivi1, Carlo Adamo1
1Laboratoire de Reconnaissance Ionique, DRFMC/LCIB (UMR_E 3 CEA-UJF), CEA-Grenoble, 17 rue des Martyrs, F-38054 Grenoble Cedex 9, France, and Laboratoire d'Électrochimie et de Chimie Analytique, CNRS UMR-7575, École Nationale Supérieure de Chimie de Paris, 11 rue P. et M. Curie, F-75231 Paris Cedex 05, France.
Abstract:
The calculation of the absorption spectra of four families of transition-metal complexes (Ni(CO)4, MnO4(-), MF6 (M = Cr, Mo, W) and CpM(CO)2 (M = Rh, Ir)) has been undertaken to unravel the influence of basis sets onto excitation energies, oscillator strengths, and assignments. Three among the most common pseudopotentials, with the corresponding valence basis sets, and two all-electron basis sets have been used for the metal center description in the framework of the time dependent Density Functional Theory (TD-DFT). Our results show that this approach does not particularly depend on the basis set used on the metal atoms. Furthermore, the chosen functional PBE0 provides transitions in good agreement with experiments, and it provides an accuracy of about 0.3 eV, comparable to that of refined post-Hartree-Fock methods.
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