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

TL;DR

This paper introduces a complex-variable MP2 method for modeling Auger spectra, offering a computationally efficient alternative to coupled-cluster approaches with comparable accuracy for core-vacant states.

Contribution

The authors develop a complex MP2 approach combined with EOM techniques to compute Auger spectra, significantly reducing computational costs while maintaining accuracy.

Findings

Accurate energies for Auger decay states comparable to EOM-CCSD.

Good agreement in decay widths and branching ratios for third-row hydrides.

Identified limitations and solutions for L$_1$-shell holes with Coster-Kronig decay.

Abstract

We model Auger spectra using second-order M\o ller-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 L$_1$-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.