ABSTRACT
For over a century, vibrational spectroscopy has enhanced the study of materials. Yet, assignment of particular molecular motions to vibrational excitations has relied on indirect methods. Here, we demonstrate that applying group theoretical methods to the dynamic pair distribution function analysis of neutron scattering data provides direct access to the individual atomic displacements responsible for these excitations. Applied to the molecule-based frustrated magnet with a potential magnetic valence-bond state, LiZn2Mo3O8, this approach allows direct assignment of the constrained rotational mode of Mo3O13 clusters and internal modes of MoO6 polyhedra. We anticipate that coupling this well known data analysis technique with dynamic pair distribution function analysis will have broad application in connecting structural dynamics to physical properties in a wide range of molecular and solid state systems.
ABSTRACT
Inelastic neutron scattering at low temperatures T≤30 K from a powder of LiZn2Mo3O8 demonstrates this triangular-lattice antiferromagnet hosts collective magnetic excitations from spin-1/2 Mo3O13 molecules. Apparently gapless (Δ<0.2 meV) and extending at least up to 2.5 meV, the low-energy magnetic scattering cross section is surprisingly broad in momentum space and involves one-third of the spins present above 100 K. The data are compatible with the presence of valence bonds involving nearest-neighbor and next-nearest-neighbor spins forming a disordered or dynamic state.
ABSTRACT
The emergence of complex electronic behaviour from simple ingredients has resulted in the discovery of numerous states of matter. Many examples are found in systems exhibiting geometric magnetic frustration, which prevents simultaneous satisfaction of all magnetic interactions. This frustration gives rise to complex magnetic properties such as chiral spin structures, orbitally driven magnetism, spin-ice behaviour exhibiting Dirac strings with magnetic monopoles, valence-bond solids and spin liquids. Here we report the synthesis and characterization of LiZn(2)Mo(3)O(8), a geometrically frustrated antiferromagnet in which the magnetic moments are localized on small transition-metal clusters rather than individual ions. By doing so, first-order Jahn-Teller instabilities and orbital ordering are prevented, allowing the strongly interacting magnetic clusters in LiZn(2)Mo(3)O(8) to probably give rise to an exotic condensed valence-bond ground state reminiscent of the proposed resonating valence-bond state. Our results also link magnetism on clusters to geometric magnetic frustration in extended solids, demonstrating a new approach for unparalleled chemical control and tunability in the search for collective, emergent electronic states of matter.