Achieving Accuracy and Economy for Calculating Vertical Detachment Energies of Molecular Anions: A Model Chemistry Composite Methods

Abstract The vertical detachment energy (VDE) is a vital factor for predicting the stability of anions that have important applications in the atom, molecule and cluster science. Due to the synthetic or characterization difficulty of anions, accurate and efficient predictions of VDE independent of laboratory data have always been an appealing task to remedy the experimental deficiencies. Unfortunately, the generally adopted CCSD(T) and electron propagator theory (EPT) methods have respectively been proven to be reliable but very cost‐expensive, and cost‐effective but sometimes problematic when Koopman's theorem is invalid. Here, we for the first time introduced and benchmarked a series of model chemistry composite methods (e. g., CBS‐QB3, G4 and W1BD) on calculating VDE for 57 molecular anions . Notably, CBS‐QB3 exceeds the accuracy of CCSD(T) while approaching the economy of EPT. Therefore, we highly recommend the composite method CBS‐QB3 to compute VDEs for molecular anions in the attractive “killing two birds with one stone” manner.