Electron excitation energies using a consistent third-order propagator approach: Comparison with full configuration interaction and coupled cluster results

Abstract

A recently developed consistent third-order propagator method for the treatment of electronic excitation in molecules is tested in first applications. The method referred to as third-order algebraic-diagrammatic construction [ADC(3)] extends the existing second-order approximation and aims at a more accurate computation of excitation energies and transition moments than afforded at the second-order level. For a stringent test of the method we compare the ADC(3) energies for over 40 singlet and triplet vertical transitions in H2O, HF, N2, and Ne with the results of recent full configuration interaction (FCI) and coupled cluster (CC) computations. The ADC(3) results reflect a substantial and uniform improvement with respect to the second-order description. The mean absolute deviation of the single excitation energies from the FCI results is below 0.2 eV. Although this does not equal the accuracy of the third-order CC3 model, the ADC(3) method, scaling as N6 with the number of orbitals, may be viewed as a good compromise between accuracy and computational cost.