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First-principles linear response theory for open quantum systems and its application to Orbach relaxation and direct magnetic relaxation in Ln-based coordination polymers

Mikolaj Zychowicz1,*, Jakub J. Zakrzewski1, Szymon Chorazy1,†, and Alessandro Lunghi2,‡

  • *Contact author: mikolaj.zychowicz@uj.edu.pl
  • †Contact author: simon.chorazy@uj.edu.pl
  • ‡Contact author: lunghia@tcd.ie
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Phys. Rev. B 114, 154424 – Published 23 September, 2026

DOI: https://doi.org/10.1103/f744-f6bq

Abstract

Single-molecule magnets (SMMs) exhibit slow magnetic relaxation as a result of axial magnetic anisotropy inhibiting spin-phonon transitions. To establish a direct link between physical observables and the microscopic theory of magnetic relaxation, we here develop and numerically implement a first-principles linear response theory for open quantum systems that provides access to the complex alternating-current (ac) magnetic susceptibility in the presence of an oscillating ac magnetic field. Once combined with density functional theory and multiconfigurational electronic structure simulations, this formalism is applied in a fully first-principles fashion to three cyanido-bridged Ln/Y-based (Ln = lanthanide) coordination polymers with general formula {LnxIIIY1−xIII[CoIII(CN)6]}, where Ln = Yb (1), Tb (2), and Dy (3). The method is able to reproduce the low-temperature direct relaxation process and its field dependence, as well as the high-temperature Orbach relaxation regime for all the investigated compounds. These results demonstrate the feasibility of ab initio simulations of magnetic ac susceptibility in lanthanide-based SMMs and support the potential of further development of ab initio open quantum systems methods toward the completion of a magnetization dynamics theory.

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Phys. Rev. B 114, 154424– Published 23 September, 2026
  • Received 7 April 2026
  • Revised 29 July 2026
  • Accepted 26 August 2026
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