Reduced-Cost Second-Order Algebraic-Diagrammatic Construction Method for Core Excitations.

Our reduced-cost scheme [ , , 094111] based on the frozen virtual natural orbital and natural auxiliary function approaches is extended to core excitations. The efficiency of the approximation is presented for the second-order algebraic-diagrammatic construction [ADC(2)] method invoking the core-valence separation (CVS) and density fitting approaches. The errors introduced by the present scheme are comprehensively analyzed for more than 200 excitation energies and 80 oscillator strengths, including C, N, and O K-edge excitations, as well as 1 → π* and Rydberg transitions. Our results show that significant savings can be gained in computational requirements at the expense of a moderate error. That is, the mean absolute error for the excitation energies, being lower than 0.20 eV, is an order of magnitude smaller than the intrinsic error of CVS-ADC(2), while the mean relative error for the oscillator strengths is between 0.06 and 0.08, which is still acceptable. As significant differences for different types of excitations cannot be observed, the robustness of the approximation is also demonstrated. The improvements in the computational requirements are measured for extended molecules. In this case, an overall 7-fold speedup is obtained in the wall-clock times, while dramatic reductions in the memory requirements are also achieved. In addition, it is also proved that the new approach enables us to perform CVS-ADC(2) calculations within reasonable runtime for systems of 100 atoms using reliable basis sets.