Finite-Field Cholesky Decomposed Coupled-Cluster Techniques (ff-CD-CC): Theory and Application to Pressure Broadening of Mg by a He Atmosphere and a Strong Magnetic Field

Abstract

For the interpretation of spectra of magnetic stellar objects such as magnetic white dwarfs (WDs) highly accurate quantum chemical predictions for atoms and molecules in finite magnetic field are required. Especially the accurate description of electronically excited states and their properties requires established methods such as those from coupled-cluster (CC) theory. However, respective calculations are computationally challenging even for medium-sized systems. Cholesky decomposition (CD) techniques may be used to alleviate memory bottlenecks. In finite-field computations, the latter are increased due to the reduction of permutational symmetry within the electron-repulsion-integrals (ERIs) as well as the need for complex-valued data types. CD enables a memory-efficient, approximate description of the ERIs with rigorous error control and thus the treatment of larger systems at the CC level becomes feasible. In order to treat molecules in a finite magnetic field (ff), we present in this work the working equations of the left and right-hand side equations for ff-EOM-CD-CCSD for various EOM flavours as well as for the approximate ff-EOM-CD-CC2 method. The methods are applied to the study of the modification of the spectral lines of a magnesium transition by a helium atmosphere that can be found in magnetic WD stars.