The approximate Coupled-Cluster methods CC2 and CC3 in a finite magnetic field

TL;DR

This paper implements and assesses the performance of approximate coupled-cluster methods CC2 and CC3 for molecules in finite magnetic fields, focusing on spectroscopic predictions and geometry optimizations relevant to highly-magnetized white dwarf atmospheres.

Contribution

It introduces the implementation of CC2 and CC3 in finite magnetic fields and evaluates their accuracy and computational efficiency for molecular properties and excited states.

Findings

ff-CC2 is a good alternative to CCSD for energies and geometries.

ff-CC2 performs well for single-excitation excited states.

ff-CC3 closely reproduces CCSDT results, enabling larger system studies.

Abstract

In this paper, we report on the implementation of CC2 and CC3 in the context of molecules in finite magnetic fields. The methods are applied to the investigation of atoms and molecules through spectroscopic predictions and geometry optimizations for the study of the atmospheres of highly-magnetized White Dwarfs (WDs). We show that ground-state finite-field (ff) CC2 is a reasonable alternative to CCSD for energies and, in particular for geometrical properties. For excited states ff-CC2 is shown to perform well for states with predominant single-excitation character. Yet, for cases in which the excited-state wavefunction has double-excitation character with respect to the reference, ff-CC2 can easily Ff-CC3, however, is shown to reproduce the CCSDT behaviour very well and enables the treatment of larger systems at a high accuracy.