Toward fast and accurate ab initio calculation of magnetic exchange in polynuclear lanthanide complexes. Issue 19 (3rd May 2019)

• Record Type: Journal Article
• Authors: Hallmen, Philipp P.; Werner, Hans-Joachim; Kats, Daniel; Lenz, Samuel; Rauhut, Guntram; Stoll, Hermann; van Slageren, Joris
• Is Part Of: Physical chemistry chemical physics. Volume 21:Issue 19(2019)
• Page Start: 9769
• Page End: 9778
• Publication Date: 2019-05-03
• Subjects: Chemistry, Physical and theoretical -- Periodicals; 541.3
• DOI: 10.1039/c9cp00785g
• Languages: English
• ISSNs: 1463-9076

Abstract

Abstract : We present an efficient ab initio methodology to calculate magnetic exchange between lanthanide ions beyond density functional theory including dynamical correlation. Abstract : Ab initio calculations of the magnetic exchange in polynuclear lanthanide complexes are very challenging and often not feasible, due to large active spaces, the large number of required states or the necessity to include dynamical correlation into the calculations. We present an approach which allows for the computationally efficient calculation of exchange splittings in polynuclear lanthanide complexes including dynamical correlation. This is achieved by extending the local-density-fitted configuration-averaged Hartree–Fock (LDF-CAHF) method to systems with more than one group of open-shell orbitals ( e.g. at different metal atoms) and combining it with linear-scaling many-state pair-natural-orbital complete active space perturbation theory of second order (PNO-CASPT2). In order to assess the performance of the method, we apply it to the asymmetric dinuclear complex [hqH2 ][Yb2 (hq)4 (NO3 )3 ]·MeOH (hqH = 8-hydroxyquinoline).