First-Principles Description of Charge Transfer in Donor-Acceptor Compounds from Self-Consistent Many-Body Perturbation Theory

TL;DR

This paper compares hybrid DFT, G0W0, and self-consistent GW methods for accurately describing charge transfer in donor-acceptor compounds, highlighting the importance of self-consistency for correct electron densities.

Contribution

It demonstrates that self-consistent GW methods improve the description of charge transfer and ground-state properties over perturbative approaches in donor-acceptor systems.

Findings

Hybrid DFT's accuracy depends on the fraction of exact exchange.

G0W0 correctly aligns frontier orbitals but doesn't modify ground-state densities.

Self-consistent GW updates electron density for accurate level alignment.

Abstract

We investigate charge transfer in prototypical molecular donor-acceptor compounds using hybrid density functional theory (DFT) and the GW approximation at the perturbative level (G0W0) and at full self-consistency (sc-GW). For the systems considered here, no charge transfer should be expected at large intermolecular separation according to photoemission experiment and accurate quantum-chemistry calculations. The capability of hybrid exchange-correlation functionals of reproducing this feature depends critically on the fraction of exact exchange $\alpha$, as for small values of $\alpha$ spurious fractional charge transfer is observed between the donor and the acceptor. G0W0 based on hybrid DFT yields the correct alignment of the frontier orbitals for all values of $\alpha$. However, G0W0 has no capacity to alter the ground-state properties of the system, because of its perturbative nature. The electron density in donor-acceptor compounds thus remains incorrect for small $\alpha$ values. In sc-GW, where the Green's function is obtained from the iterative solution of the Dyson equation, the electron density is updated and reflects the correct description of the level alignment at the GW level, demonstrating the importance of self-consistent many-body approaches for the description of ground- and excited-state properties in donor-acceptor systems.