$S$ = 1/2 ferromagnetic-antiferromagnetic alternating Heisenberg chain in a zinc-verdazyl complex

TL;DR

This study synthesizes and characterizes a zinc-verdazyl complex as an ideal model for an $S=1/2$ ferromagnetic-antiferromagnetic alternating Heisenberg chain, revealing a Haldane gap through experimental and computational analysis.

Contribution

It provides the first experimental realization and detailed analysis of an $S=1/2$ F-AF Heisenberg chain with evidence of a Haldane gap in a zinc-verdazyl complex.

Findings

Observation of a zero-field excitation gap of 0.5 T.

Magnetic susceptibility and specific heat show thermally activated behavior below 1 K.

Quantum Monte Carlo calculations confirm the F-AF chain model with a ratio |J_AF/J_F| = 0.22.

Abstract

We successfully synthesized the zinc-verdazyl complex [Zn(hfac)$_2$]$\cdot$($o$-Py-V) [hfac = 1,1,1,5,5,5-hexafluoroacetylacetonate; $o$-Py-V = 3-(2-pyridyl)-1,5-diphenylverdazyl], which is an ideal model compound with an $S$ = 1/2 ferromagnetic-antiferromagnetic alternating Heisenberg chain (F-AF AHC). $Ab$ $initio$ molecular orbital (MO) calculations indicate that two dominant interactions $J_{\rm{F}}$ and $J_{\rm{AF}}$ form the $S=1/2$ F-AF AHC in this compound. The magnetic susceptibility and magnetic specific heat of the compound exhibit thermally activated behavior below approximately 1 K. Furthermore, its magnetization curve is observed up to the saturation field and directly indicates a zero-field excitation gap of 0.5 T. These experimental results provide evidence for the existence of a Haldane gap. We successfully explain the results in terms of the $S=1/2$ F-AF AHC through quantum Monte Carlo calculations with $|J_{\rm{AF}}/J_{\rm{F}}|$ = 0.22. The $ab$ $initio$ MO calculations also indicate a weak AF interchain interaction $J'$ and that the coupled F-AF AHCs form a honeycomb lattice. The $J'$ dependence of the Haldane gap is calculated, and the actual value of $J'$ is determined to be less than 0.01$|J_{\rm{F}}|$.