Complex-variable MP2 theory applied to core-vacant states for the computation of Auger spectra

Abstract

We model Auger spectra using second-order Møller–Plesset perturbation (MP2) theory combined with complex-scaled basis functions. For this purpose, we decompose the complex MP2 energy of the core-hole state into contributions from specific decay channels and propose a corresponding equation-of-motion (EOM) method for computing the doubly ionized final states of Auger decay. These methods lead to significant savings in computational cost compared to our recently developed approaches based on coupled-cluster theory [F. Matz and T.-C. Jagau, J. Chem. Phys. 156, 114117 (2022)]. The test set for this study comprises water, ammonia, methane, hydrogen sulfide, phosphine, and silane. The energies of the final states of Auger decay are obtained with an accuracy comparable to EOM coupled-cluster singles and doubles (CCSD) theory. Partial decay widths and branching ratios between KLL, KLM, and KMM decay of K-shell holes in third-row hydrides are in good agreement with EOM-CCSD, while deviations are more significant for second-row hydrides. For L1-shell holes, which undergo Coster–Kronig decay, MP2 yields unphysical results. However, we show that a suitable shift of the MP2 energy denominators leads to more reliable branching ratios and spectra for these problematic cases.