Intersystem-crossing and phosphorescence rates in fac-Ir(III)(ppy)3: a theoretical study involving multi-reference configuration interaction wavefunctions

The Journal of Chemical Physics
Martin KleinschmidtChristel M Marian

Abstract

We have employed combined density functional theory and multi-reference configuration interaction methods including spin-orbit coupling (SOC) effects to investigate the photophysics of the green phosphorescent emitter fac-tris-(2-phenylpyridine)iridium (fac-Ir(ppy)3). A critical evaluation of our quantum chemical approaches shows that a perturbational treatment of SOC is the method of choice for computing the UV/Vis spectrum of this heavy transition metal complex while multi-reference spin-orbit configuration interaction is preferable for calculating the phosphorescence rates. The particular choice of the spin-orbit interaction operator is found to be of minor importance. Intersystem crossing (ISC) rates have been determined by Fourier transformation of the time correlation function of the transition including Dushinsky rotations. In the electronic ground state, fac-Ir(ppy)3 is C3 symmetric. The calculated UV/Vis spectrum is in excellent agreement with experiment. The effect of SOC is particularly pronounced for the metal-to-ligand charge transfer (MLCT) band in the visible region of the absorption spectrum which does not only extend its spectral onset towards longer wavelengths but also experiences a blue shift of its maximum....Continue Reading

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Citations

Feb 26, 2016·Inorganic Chemistry·Thomas HofbeckHartmut Yersin
Jan 4, 2017·Journal of Chemical Theory and Computation·Fabian DinkelbachChristel M Marian
Apr 8, 2017·Chemical Reviews·Gleb BaryshnikovHans Ågren
Jun 9, 2018·Chemistry : a European Journal·Carmen SousaCoen de Graaf
Jan 30, 2020·Physical Chemistry Chemical Physics : PCCP·Jelena FöllerChristel M Marian
Sep 11, 2019·Physical Chemistry Chemical Physics : PCCP·Adrian Heil, Christel M Marian
Apr 5, 2020·Molecules : a Journal of Synthetic Chemistry and Natural Product Chemistry·Mario BrackerChristel M Marian
Dec 16, 2020·Physical Chemistry Chemical Physics : PCCP·Torsha MoitraSwapan Chakrabarti
Feb 21, 2021·Annual Review of Physical Chemistry·Christel M Marian
Apr 26, 2019·Inorganic Chemistry·Adrian Heil, Christel M Marian
Sep 26, 2017·The Journal of Physical Chemistry Letters·Lopa PaulKenneth Ruud
Jun 7, 2018·The Journal of Physical Chemistry. a·Xiang-Yang LiuGanglong Cui
Jan 9, 2019·The Journal of Physical Chemistry Letters·Lopa PaulSwapan Chakrabarti
Jul 17, 2018·The Journal of Physical Chemistry Letters·Lopa PaulSwapan Chakrabarti
Aug 3, 2017·The Journal of Physical Chemistry Letters·Andrew J Atkins, Leticia González
Oct 24, 2020·The Journal of Physical Chemistry Letters·Hai BiSemion K Saikin
Sep 2, 2021·JACS Au·J Patrick Zobel, Leticia González
Nov 19, 2021·Journal of Chemical Theory and Computation·Rulin FengJochen Autschbach
Aug 25, 2017··Christoph A. JungemannChristoph Zimmermann

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