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The singlet-triplet splittings of a set of diradical organic molecules are calculated using multiconfiguration pair-density functional theory (MC-PDFT) and the results are compared with those obtained by Kohn-Sham density functional theory (KS-DFT) and complete active space second-order perturbation theory (CASPT2) calculations. We found that MC-PDFT, even with small and systematically defined active spaces, is competitive in accuracy with CASPT2, and it yields results with greater accuracy and precision than Kohn-Sham DFT with the same parent functional. MC-PDFT also avoids the challenges associated with spin contamination in KS-DFT. It is also shown that MC-PDFT is much less computationally expensive than CASPT2 when applied to larger active spaces, and this illustrates the promise of this method for larger diradical organic systems.


Originally published as:

Stoneburner, S. J.; Truhlar, D. G.; Gagliardi, L. MC-PDFT Can Calculate Singlet-Triplet Splittings of Organic Diradicals. J. Chem. Phys. 2018, 148, 064108.

Stoneburner, S. J., Truhlar, D. G., & Gagliardi, L. (2018). MC-PDFT can calculate singlet–triplet splittings of organic diradicals. The Journal of Chemical Physics, 148(6), 064108.