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Niehaus, Thomas A. ; Hofbeck, T. ; Yersin, Hartmut

Charge-transfer excited states in phosphorescent organo-transition metal compounds: a difficult case for time dependent density functional theory?

Artikel

Niehaus, Thomas A., Hofbeck, T. und Yersin, Hartmut (2015) Charge-transfer excited states in phosphorescent organo-transition metal compounds: a difficult case for time dependent density functional theory? RSC Advances 5, S. 63318.

DOI zum Zitieren dieses Dokuments: 10.5283/epub.32254


Zusammenfassung

Light emitting organo-transition metal complexes have found widespread use in the past. The computational modelling of such compounds is often based on time-dependent density functional theory (TDDFT), which enjoys popularity due to its numerical efficiency and simple black-box character. It is well known, however, that TDDFT notoriously underestimates energies of charge-transfer excited states ...

Light emitting organo-transition metal complexes have found widespread use in the past. The computational modelling of such compounds is often based on time-dependent density functional theory (TDDFT), which enjoys popularity due to its numerical efficiency and simple black-box character. It is well known, however, that TDDFT notoriously underestimates energies of charge-transfer excited states which are prominent in phosphorescent metal–organic compounds. In this study, we investigate whether TDDFT is providing a reliable description of the electronic properties in these systems. To this end, we compute 0–0 triplet state energies for a series of 17 pseudo-square planar platinum(II) and pseudo-octahedral iridium(III) complexes that are known to feature quite different localization characteristics ranging from ligand-centered (LC) to metal-to-ligand charge transfer (MLCT) transitions. The calculations are performed with conventional semi-local and hybrid functionals as well as with optimally tuned range-separated functionals that were recently shown to overcome the charge transfer problem in TDDFT. We compare our results against low temperature experimental data and propose a criterion to classify excited states based on wave function localization. In addition, singlet absorption energies and singlet–triplet splittings are evaluated for a subset of the compounds and are also validated against experimental data. Our results indicate that for the investigated complexes charge-transfer is much less pronounced than previously believed.



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Details

DokumentenartArtikel
Titel eines Journals oder einer ZeitschriftRSC Advances
VerlagRoyal Society of Chemistry
Band5
SeitenbereichS. 63318
Datum10 Juli 2015
Veröffentlichungsdatum27 Jul 2015 09:03
Zusätzliche Informationen (Öffentlich)Open Access Komponente aus der Allianzlizenz
InstitutionenPhysik > Institut für Theoretische Physik > Entpflichtete oder im Ruhestand befindliche Professoren > Arbeitsgruppe Thomas Niehaus
Chemie und Pharmazie > Institut für Physikalische und Theoretische Chemie > Chair of Chemistry III - Physical Chemistry (Molecular Spectroscopy and Photochemistry) > Prof. Dr. Hartmut Yersin
Identifikationsnummer
WertTyp
10.1039/C5RA12962ADOI
Dewey-Dezimal-Klassifikation500 Naturwissenschaften und Mathematik > 530 Physik
500 Naturwissenschaften und Mathematik > 540 Chemie
StatusVeröffentlicht
BegutachtetJa, diese Version wurde begutachtet
An der Universität Regensburg entstandenJa
URN der UB Regensburgurn:nbn:de:bvb:355-epub-322547
Dokumenten-ID32254

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