Extrapolating Unconverged GW Energies up to the Complete Basis Set Limit with Linear Regression

摘要

The GW approximation to the electronic self-energy is now a well-recognized approach to obtain the electron quasiparticle energies of molecules and, in particular, their ionization potential and electron affinity. Though much faster than the corresponding wavefunction methods, the GW energies are still affected by slow convergence with respect to the basis completeness. This limitation hinders a wider application of the GW approach. Here, we show that we can reach the complete basis set limit for the cumbersome GW calculations solely based on fast preliminary calculations with an unconverged basis set. We introduce a linear model that correlates the molecular orbital characteristics and the basis convergence error for a large database of approximately 600 states in 104 organic molecules that contain H, C, O, N, F, P, S, and Cl. The model employs molecular-orbital-based non-linear descriptors that encode efficiently the chemical space offering outstanding transferability. Using a low number of descriptors (17) the performance of this extrapolation procedure is superior to that of the earlier more physically motivated approaches. The predictive power of the method is finally demonstrated for a selection of large acceptor molecules.