Influence of triplet instabilities in TDDFT
Michael J. G. Peach, Matthew J. Williamson, David J. Tozer, J. Chem. Theory Comput., 7, 3578–3585, 2011.
Commentary
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Citations
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In our first major investigation of triplet excited states, we considered the difference in behaviour highlighted by Jacquemin and co-workers, between the exact exchange-dependence of singlet and triplet excited states. We showed (in a re-discovery of problems known from Hartree–Fock theory) that triplet states are plagued by instabilities (or near-instabilities) from the ground-state wavefunction. The problems are exacerbated as the amount of exact exchange in a functional increases. The Tamm–Dancoff approximation was shown to provide significant improvements for both singlet and triplet states of character similar to the wavefunction instabilities.
We are currently following up this work on a more demanding, newly developed benchmark set, and we link the instability problem to Lambda. Watch this space!
Further information, including details of subsequent work in this area, can be found on the TDDFT diagnostic research page. For the abstract, and access to the full text, see below.
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