Spin-Free CC2 Implementation of Induced Transitions between Singlet Ground and Triplet Excited States

Benjamin Helmich-Paris∗†‡, Christof Hättig ∗†, and Christof van Wüllen∗§,

Lehrstuhl für Theoretische Chemie; Ruhr-Universität Bochum, 44801 Bochum, Germany
Section of Theoretical Chemistry, VU University Amsterdam, De Boelelaan 1083, 1081 HV Amsterdam, The Netherlands
§TU Kaiserslautern, FB Chemie und Forschungszentrum OPTIMAS, Erwin-Schrödinger-Str. 52, D-67663 Kaiserslautern

J. Chem. Theory. Comput. 12, 1892-1904 (2016).
Publication Date (Web): February 16, 2016

In most organic molecules, phosphorescence has its origin in transitions from triplet exited states to the singlet ground state, which are spin-forbidden in nonrelativistic quantum mechanics. A sufficiently accurate description of phosphorescence lifetimes for molecules that contain only light elements can be achieved by treating the spin-orbit coupling (SOC) with perturbation theory (PT). We present an efficient implementation of this approach for the approximate coupled cluster singles and doubles model CC2 in combination with the resolution-of-the-identity approximation for the electron repulsion integrals. The induced oscillator strengths and phosphorescence lifetimes from SOC-PT are computed within the response theory framework. In contrast to previous work, we employ an explicitly spin-coupled basis for singlet and triplet operators. Thereby, a spin-orbital treatment can be entirely avoided for closed-shell molecules. For compounds containing only light elements, the phosphorescence lifetimes obtained with SOC-PT-CC2 are in good agreement with those of exact two-component (X2C) CC2, whereas the calculations are roughly 12 times faster than with X2C. Phosphorescence lifetimes computed for two thioketones with the SOC-PT-CC2 approach agree very well with reference results from experiment and are similar to those obtained with multireference spin-orbit configuration interaction and with X2C-CC2. An application to phosphorescent emitters for metal-free organic light-emitting diodes (OLEDs) with almost 60 atoms and more than 1800 basis functions demonstrates how the approach extends the applicability of coupled cluster methods for studying phosphorescence. The results indicate that other decay channels like vibrational relaxation may become important in such systems if lifetimes are large.

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