Simplified GW/BSE Approach for Charged and Neutral Excitation Energies of Large Molecules and Nanomaterials

Inspired by Grimme's simplified Tamm-Dancoff 138, 244104], we describe a simplified approach to excited-state calculations within the GW approximation to the self-energy and the Bethe-Salpeter equation (BSE), which we call sGW/sBSE. The primary simplification to the electron repulsion integrals yields the same structure as with tensor hypercontraction, such that our method has a storage requirement that grows quadratically with system size and computational timing that grows cubically with system size. The performance of sGW is tested on the ionization potential of the molecules in the GW100 test set, for which it differs from ab initio GW calculations by only 0.2 eV. The performance of sBSE (based on the sGW input) is tested on the excitation energies of molecules in Thiel's set, for which it differs from ab initio GW/BSE calculations by about 0.5 eV. As examples of the systems that can be routinely studied with sGW/sBSE, we calculate the band gap and excitation energy of hydrogen-passivated silicon nanocrystals with up to 2650 electrons in 4678 spatial orbitals and the absorption spectra of two large organic dye molecules with hundreds of atoms.

Automated summary

This article introduces a simplified approach to excited-state calculations within the GW approximation to the self-energy and the Bethe-Salpeter equation (BSE), called sGW/sBSE. The method is tested and verified for its performance in calculating ionization potential and excitation energies of molecules. It demonstrates small storage requirements and computational timing when used for larger systems.