Muon–Nitrogen Quadrupolar Level Crossing Resonance in a Charge Transfer Salt

[Image: see text] Although muons are primarily regarded as a local spin probe, they can also access the charge state of an atom or molecule via quadrupolar level crossing resonance (QLCR) spectroscopy. We use Li(+)TCNQ(–) (TCNQ = 7,7,8,8-tetracyanoquinodimethane), a simple charge transfer salt, to test the potential of this technique in molecular systems by studying the interaction of a positive muon with the TCNQ nitrogen atoms. We show that both a positive muon and muonium are able to add to the nitrogen, leading to a singlet spin state for the addition molecule. This produces a characteristic three line QLCR spectrum, with the observed line positions and intensities determined by the principal values and orientation of the electric field gradient tensor at the nitrogen. Ab initio calculation of this field gradient and the resulting QLCR spectrum give good agreement with the experiment. A nonresonant background contribution to the relaxation rate also provides evidence for spin excitations rapidly diffusing along the TCNQ chains. These reflect mobile unpaired electrons introduced by muonium addition. It is thus shown that a single set of muon measurements can be sensitive to both spin and charge degrees of freedom in the same molecular material.