Chemically accurate singlet-triplet gaps of organic chromophores and linear acenes by the random phase approximation and σ-functionals

Abstract

Predicting the energy differences between different spin-states is challenging for many widely used ab initio electronic structure methods. We here assess the ability of the direct random phase approximation (dRPA), dRPA plus two different screened second-order exchange (SOX) corrections, and σ-functionals to predict adiabatic singlet-triplet gaps. With mean absolute deviations of below 0.1 eV to experimental reference values, independent of the Kohn–Sham starting point, dRPA and σ-functionals accurately predict singlet-triplet gaps of 18 organic chromophores. The addition of SOX corrections to dRPA considerably worsens agreement with experiment, adding to the mounting evidence that dRPA+SOX methods are not generally applicable beyond-RPA methods. Also for a series of linear acene chains with up to ten fused rings, dRPA, and σ-functionals are in excellent agreement with coupled-cluster single double triple reference data. In agreement with advanced multi-reference methods, dRPA@PBE and σ-functional@PBE predict a singlet ground state for all chain lengths, while dRPA@PBE0 and σ-functional@PBE0 predict a triplet ground state for longer acenes. Our work shows dRPA and σ-functionals to be reliable methods for calculating singlet-triplet gaps in aromatic molecules.