Exploring non-covalent interactions in excited states: beyond aromatic excimer models

Abstract

Time-dependent Density Functional Theory (TD-DFT) offers a relatively accurate and inexpensive approach for excited state calculations. However, conventional TD-DFT may suffer from the same poor description of non-covalent interactions (NCIs) which is known from ground-state DFT. In this work we present a comprehensive benchmark study of TD-DFT for excited-state NCIs. This is achieved by calculating dissociation curves for excited complexes (‘exciplexes’), whose binding strength depends on excited-state NCIs including electrostatics, Pauli repulsion, charge-transfer, exciton coupling, and London dispersion. Reference dissociation curves are calculated with the reasonably accurate wave function method SCS-CC2/CBS(3,4) which is used to benchmark a range of TD-DFT methods. Additionally, we test the effect of ground-state dispersion corrections, DFT-D3(BJ) and VV10, for exciplex binding. Overall, we find that TD-DFT methods generally under-bind exciplexes which can be explained by the missing dispersion forces. Underbinding errors reduce going up the rungs of Jacob’s ladder. Further, the D3(BJ) dispersion correction is essential for good accuracy in most cases. Likewise, the VV10-type non-local kernel yields relatively low errors and has comparable performance in either its fully self-consistent implementation or as a post-SCF additive correction, but its impact is solely on ground-state energies and not on excitation energies. From our analysis, the most robust TD-DFT methods for exciplexes with localised excitations in their equilibrium and non-equilibrium geometries are the double hybrids B2GP-PLYP-D3(BJ) and B2PLYP-D3(BJ). Their range-separated versions ωB2(GP-)PLYP-D3(BJ) or the spin-opposite scaled, range-separated double hybrid SOS-ωB88PP86 can be recommended when charge transfer plays a role in the excitations. We also identify the need for a state-specific dispersion correction as the next step for improved TD-DFT performance.