Assessment of Charge-Transfer Excitations in Organic Dyes obtained from TD-srDFT Based on Long-Range MP2 and MCSCF Wave Functions

TL;DR

This paper evaluates the effectiveness of combining wave function methods with short-range DFT in describing charge transfer excitations, showing improved accuracy over traditional TD-DFT, especially for multireference systems like retinal.

Contribution

It introduces and tests a novel combination of MCSCF and SOPPA with short-range DFT for charge transfer excitations, demonstrating improved accuracy and applicability to multireference molecules.

Findings

TD-MC-srDFT yields good agreement with reference data.

SOPPA-srDFT performs slightly better on benchmark molecules.

Accurately describes multireference states like retinal chromophore.

Abstract

Charge transfer excitations can be described within TD-DFT, not only by means of long-range corrected exchange functionals but also with a combination of wave function theory and TD-DFT based on range separation. The latter approach enables a rigorous formulation of multi-determinantal TD-DFT schemes where excitation classes, which are absent in conventional TD-DFT spectra (like for example double excitations), can be addressed. This paper investigates the combination of both the long-range MCSCF and SOPPA ans\"atze with a short-range DFT (srDFT) description. We find that the combinations of SOPPA or MCSCF with TD-DFT yield better results than could be expected from the pure wave function schemes. For the Time-Dependent MCSCF short-range DFT ansatz (TD-MC-srDFT) excitation energies calculated over a larger benchmark set of molecules with predominantly single reference character yield good agreement with their reference values, and are in general comparable to the long-range corrected functional CAM-B3LYP. The SOPPA-srDFT scheme is tested for a subset of molecules used for benchmarking TD-MC-srDFT and performs slightly better against the reference data for this small subset. Beyond the proof-of-principle calculations comprising the first part of this contribution, we additionally studied the low-lying singlet excited states (S1 and S2) of the retinal chromophore. The chromophore displays multireference character in the ground state and both excited states exhibit considerable double excitation character, which in turn cannot be described within standard TD-DFT, due to the adiabatic approximation. However, a TD-MC-srDFT approach can account for the multireference character, and excitation energies are obtained with accuracy comparable to CASPT2, although using a much smaller active space.