Relativistic Exact-Two-Component Core-Valence-Separated Algebraic Diagrammatic Construction Theory For Near L-edge X-ray Absorption Spectra

TL;DR

This paper introduces an efficient relativistic CVS-ADC(2) method for core-excitation calculations, optimized for heavy elements, with demonstrated accuracy and computational savings over traditional approaches.

Contribution

The authors develop a two-component relativistic CVS-ADC(2) implementation using SA-FNS and Cholesky decomposition, reducing computational cost while maintaining accuracy.

Findings

Benchmarking confirms reliability against four-component calculations.

Close agreement with canonical results demonstrates accuracy.

Application to transition-metal compounds and a ruthenium complex shows practical utility.

Abstract

We present an efficient implementation of the second-order two-component relativistic core-valence-separated algebraic diagrammatic construction method (CVS-ADC(2)) for core-excitation calculations. The approach employs state-averaged frozen natural spinors (SA-FNS) to reduce the number of floating-point operations, together with the Cholesky decomposition (CD) technique, which lowers the storage requirements associated with two-electron integrals. These reductions make the method particularly well-suited for systems containing heavy elements. Systematic benchmarking against four-component reference calculations confirms the reliability and robustness of the two-component (X2CMP/X2CAMF)-based framework. The close agreement with canonical results further demonstrates that the SA-FNS-based CVS-ADC(2) approach achieves comparable accuracy at only a fraction of the computational cost. Moreover, benchmark studies of L$_{2,3}$-edge spectra for 3$d$ transition-metal compounds demonstrate that CVS-ADC(2) serves as a computationally efficient and reliable alternative to the non-Hermitian EOM-CC method for reproducing experimental spectra. Finally, calculations on a ruthenium complex illustrate the method's applicability to relativistic studies of medium-sized molecular systems.