The mechanism of magnetic interactions in the bulk ferromagnet para-(methylthio)phenyl nitronyl nitroxide (YUJNEW): A first principles, bottom-up, theoretical study

Abstract

The mechanism of magnetic interactions in the bulk ferromagnet para-(methylthio)phenyl nitronyl nitroxide crystal (YUJNEW) has been theoretically reinvestigated, using only data from ab initio calculations and avoiding any a priori assumptions. We first calculate the microscopic magnetic interactions (J AB exchange couplings) between all unique radical pairs in the crystal, and then generate the macroscopic magnetic properties from the energy levels of the corresponding Heisenberg Hamiltonian. We thus propose a first principles, bottom-up (i.e. micro-to-macro) approach that brings theory and experiment together. We have applied this strategy to study the magnetism of YUJNEW using data from the previously reported 298 and 114 K crystal structures, and also data from a 10 K neutron diffraction structure fully reported in this work. The magnetic topology at 298 K is two-dimensional : noninteracting planes, with three different in-plane J AB pair interactions (+0.24, +0.09, and -0.11 cm -1) and one numerically negligible (+0.02 cm -1) inter-plane J AB interaction. In contrast, the magnetic topology at 114 and 10 K is three-dimensional, with two non-negligible in-plane J AB constants (+0.11 and +0.07 cm -1 at 114 K; +0.22 and +0.07 cm -1 at 10 K) and one interplane pair interaction (+ 0.07 cm -1 at 114 K; +0.08 cm -1 at 10 K). Although this three-dimensional magnetic topology is consistent with YUJNEW being a bulk ferromagnet, there is only a qualitative agreement between computed and experimental magnetic susceptibility χT(T) data at 114 K. However, the experimental χT(T) curve is quantitatively reproduced at 10 K. The heat capacity curve presents a peak at around 0.12 K, close to the estimated experimental peak (0.20 K).