Quasiparticle Self-Consistent GW-Bethe-Salpeter Equation Calculations for Large Chromophoric Systems

The GW-Bethe-Salpeter equation (BSE) method is promising for calculating the low-lying excitonic states of molecular systems. However, so far it has only been applied to rather small molecules and in the commonly implemented diagonal approximations to the electronic self-energy, it depends on a mean-field starting point. We describe here an implementation of the self-consistent and starting-point-independent quasiparticle self-consistent (qsGW)-BSE approach, which is suitable for calculations on large molecules. We herein show that eigenvalue-only self-consistency can lead to an unfaithful description of some excitonic states for chlorophyll dimers while the qsGW-BSE vertical excitation energies (VEEs) are in excellent agreement with spectroscopic experiments for chlorophyll monomers and dimers measured in the gas phase. Furthermore, VEEs from time-dependent density functional theory calculations tend to disagree with experimental values and using different range-separated hybrid (RSH) kernels does change the VEEs by up to 0.5 eV. We use the new qsGW-BSE implementation to calculate the lowest excitation energies of the six chromophores of the photosystem II (PSII) reaction center (RC) with nearly 2000 correlated electrons. Using more than 11,000 (6000) basis functions, the calculation could be completed in less than 5 (2) days on a single modern compute node. In agreement with previous TD-DFT calculations using RSH kernels on models that also do not include environmental effects, our qsGW-BSE calculations only yield states with local characters in the low-energy spectrum of the hexameric complex. Earlier works with RSH kernels have demonstrated that the protein environment facilitates the experimentally observed interchromophoric charge transfer. Therefore, future research will need to combine correlation effects beyond TD-DFT with an explicit treatment of environmental electrostatics.

Automated summary

The study introduces a self-consistent and starting-point-independent qsGW-BSE method for calculations on large molecules, demonstrating its excellent agreement with experimental results for vertical excitation energies of chlorophyll monomers and dimers. Calculations on photosystem II reaction centers using this method show low-energy spectra with local character states.