# Intersystem-crossing and phosphorescence rates in fac-Ir{sup III}(ppy){sub 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){sub 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){sub 3} is C{sub 3} 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. Pseudo-Jahn-Teller interaction leads to asymmetric coordinate displacements in the lowest MLCT states. Substantial electronic SOC and a small energy gap make ISC an ultrafast process in fac-Ir(ppy){sub 3}. Formore »

- Authors:

- Institute of Theoretical and Computational Chemistry, Heinrich-Heine-University Düsseldorf, Universitätsstraße 1, 40225 Düsseldorf (Germany)
- Fachbereich Chemie and Forschungszentrum OPTIMAS, Technical University of Kaiserslautern, Erwin-Schrödinger-Straße 52, 67663 Kaiserslautern (Germany)

- Publication Date:

- OSTI Identifier:
- 22416215

- Resource Type:
- Journal Article

- Resource Relation:
- Journal Name: Journal of Chemical Physics; Journal Volume: 142; Journal Issue: 9; Other Information: (c) 2015 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA)

- Country of Publication:
- United States

- Language:
- English

- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ABSORPTION SPECTRA; COMPLEXES; CONFIGURATION INTERACTION; CORRELATION FUNCTIONS; COUPLING; DENSITY FUNCTIONAL METHOD; DIPOLE MOMENTS; ENERGY GAP; FINE STRUCTURE; FOURIER TRANSFORMATION; GROUND STATES; IRIDIUM COMPOUNDS; JAHN-TELLER EFFECT; LIGANDS; METHYLENE CHLORIDE; PHOSPHORESCENCE; PYRIDINES; REACTION KINETICS; SPIN; WAVE FUNCTIONS

### Citation Formats

```
Kleinschmidt, Martin, Marian, Christel M., E-mail: Christel.Marian@hhu.de, and Wüllen, Christoph van.
```*Intersystem-crossing and phosphorescence rates in fac-Ir{sup III}(ppy){sub 3}: A theoretical study involving multi-reference configuration interaction wavefunctions*. United States: N. p., 2015.
Web. doi:10.1063/1.4913513.

```
Kleinschmidt, Martin, Marian, Christel M., E-mail: Christel.Marian@hhu.de, & Wüllen, Christoph van.
```*Intersystem-crossing and phosphorescence rates in fac-Ir{sup III}(ppy){sub 3}: A theoretical study involving multi-reference configuration interaction wavefunctions*. United States. doi:10.1063/1.4913513.

```
Kleinschmidt, Martin, Marian, Christel M., E-mail: Christel.Marian@hhu.de, and Wüllen, Christoph van. Sat .
"Intersystem-crossing and phosphorescence rates in fac-Ir{sup III}(ppy){sub 3}: A theoretical study involving multi-reference configuration interaction wavefunctions". United States.
doi:10.1063/1.4913513.
```

```
@article{osti_22416215,
```

title = {Intersystem-crossing and phosphorescence rates in fac-Ir{sup III}(ppy){sub 3}: A theoretical study involving multi-reference configuration interaction wavefunctions},

author = {Kleinschmidt, Martin and Marian, Christel M., E-mail: Christel.Marian@hhu.de and Wüllen, Christoph van},

abstractNote = {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){sub 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){sub 3} is C{sub 3} 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. Pseudo-Jahn-Teller interaction leads to asymmetric coordinate displacements in the lowest MLCT states. Substantial electronic SOC and a small energy gap make ISC an ultrafast process in fac-Ir(ppy){sub 3}. For the S{sub 1}↝T{sub 1} non-radiative transition, we compute a rate constant of k{sub ISC} = 6.9 × 10{sup 12} s{sup −1} which exceeds the rate constant of radiative decay to the electronic ground state by more than six orders of magnitude, in agreement with the experimental observation of a subpicosecond ISC process and a triplet quantum yield close to unity. As a consequence of the geometric distortion in the T{sub 1} state, the T{sub 1} → S{sub 0} transition densities are localized on one of the phenylpyridyl moieties. In our best quantum chemical model, we obtain phosphorescence decay times of 264 μs, 13 μs, and 0.9 μs, respectively, for the T{sub 1,I}, T{sub 1,II}, and T{sub 1,III} fine-structure levels in dichloromethane (DCM) solution. In addition to reproducing the correct orders of magnitude for the individual phosphorescence emission probabilities, our theoretical study gives insight into the underlying mechanisms. In terms of intensity borrowing from spin-allowed transitions, the low emission probability of the T{sub 1,I} substate is caused by the mutual cancellation of contributions from several singlet states to the total transition dipole moment. Their contributions do not cancel but add up in case of the much faster T{sub 1,III} → S{sub 0} emission while the T{sub 1,II} → S{sub 0} emission is dominated by intensity borrowing from a single spin-allowed process, i.e., the S{sub 2} → S{sub 0} transition.},

doi = {10.1063/1.4913513},

journal = {Journal of Chemical Physics},

number = 9,

volume = 142,

place = {United States},

year = {Sat Mar 07 00:00:00 EST 2015},

month = {Sat Mar 07 00:00:00 EST 2015}

}