Intersystem-crossing and phosphorescence rates in fac-Ir(III)(ppy)3: a theoretical study involving multi-reference configuration interaction wavefunctions
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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DFT/MRCI-R2018 study of the photophysics of the zinc(ii) tripyrrindione radical: non-Kasha emission?
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