Alternant Hydrocarbon Diradicals as Optically Addressable Molecular Qubits

High-spin molecules allow for bottom-up qubit design and are promising platforms for magnetic sensing and quantum information science. Optical addressability of molecular electron spins has also been proposed in first-row transition metal complexes via optically-detected magnetic resonance (ODMR) mechanisms analogous to the diamond-NV colour centre. However, significantly less progress has been made on the front of metal-free molecules, which can deliver lower costs and milder environmental impacts. At present, most luminescent open-shell organic molecules are $\pi$-diradicals, but such systems often suffer from poor ground-state open-shell characters necessary to realise a stable ground-state molecular qubit. In this work, we use alternancy symmetry to selectively minimise radical-radical interactions in the ground state, generating $\pi$-systems with high diradical characters. We call them m-dimers, referencing the need to covalently link two benzylic radicals at their meta carbon atoms for the desired symmetry. Through a detailed electronic structure analysis, we find that the excited states of alternant hydrocarbon m-diradicals contain important symmetries that can be used to construct ODMR mechanisms leading to ground-state spin polarisation. The molecular parameters are set in the context of a tris(2,4,6-trichlorophenyl)methyl (TTM) radical dimer covalently tethered at the meta position, demonstrating the feasibility of alternant m-diradicals as molecular colour centres.Comment: 12 pages, 5 figures, 1 table. Minor edits made to the manuscript tex

Strain fields in twisted bilayer graphene

Van der Waals heteroepitaxy allows deterministic control over lattice mismatch or azimuthal orientation between atomic layers to produce long wavelength superlattices. The resulting electronic phases depend critically on the superlattice periodicity as well as localized structural deformations that introduce disorder and strain. Here, we introduce Bragg interferometry, based on four-dimensional scanning transmission electron microscopy, to capture atomic displacement fields in twisted bilayer graphene with twist angles < 2{\deg}. Nanoscale spatial fluctuations in twist angle and uniaxial heterostrain are statistically evaluated, revealing the prevalence of short-range disorder in this class of materials. By quantitatively mapping strain tensor fields we uncover two distinct regimes of structural relaxation -- in contrast to previous models depicting a single continuous process -- and we disentangle the electronic contributions of the rotation modes that comprise this relaxation. Further, we find that applied heterostrain accumulates anisotropically in saddle point regions to generate distinctive striped shear strain phases. Our results thus establish the reconstruction mechanics underpinning the twist angle dependent electronic behaviour of twisted bilayer graphene, and provide a new framework for directly visualizing structural relaxation, disorder, and strain in any moir\'e material.Comment: 29 pages, 6 figures plus supporting information (42 pages, 28 figures

Strain fields in twisted bilayer graphene.

Van der Waals heteroepitaxy allows deterministic control over lattice mismatch or azimuthal orientation between atomic layers to produce long-wavelength superlattices. The resulting electronic phases depend critically on the superlattice periodicity and localized structural deformations that introduce disorder and strain. In this study we used Bragg interferometry to capture atomic displacement fields in twisted bilayer graphene with twist angles &lt;2°. Nanoscale spatial fluctuations in twist angle and uniaxial heterostrain were statistically evaluated, revealing the prevalence of short-range disorder in moiré heterostructures. By quantitatively mapping strain tensor fields, we uncovered two regimes of structural relaxation and disentangled the electronic contributions of constituent rotation modes. Further, we found that applied heterostrain accumulates anisotropically in saddle-point regions, generating distinctive striped strain phases. Our results establish the reconstruction mechanics underpinning the twist-angle-dependent electronic behaviour of twisted bilayer graphene and provide a framework for directly visualizing structural relaxation, disorder and strain in moiré materials

Hard Ferromagnetism Down to the Thinnest Limit of Iron-Intercalated Tantalum Disulfide.

Two-dimensional (2D) magnetic crystals hold promise for miniaturized and ultralow power electronic devices that exploit spin manipulation. In these materials, large, controllable magnetocrystalline anisotropy (MCA) is a prerequisite for the stabilization and manipulation of long-range magnetic order. In known 2D magnetic crystals, relatively weak MCA typically results in soft ferromagnetism. Here, we demonstrate that ferromagnetic order persists down to the thinnest limit of FexTaS2 (Fe-intercalated bilayer 2H-TaS2) with giant coercivities up to 3 T. We prepare Fe-intercalated TaS2 by chemical intercalation of van der Waals-layered 2H-TaS2 crystals and perform variable-temperature transport, transmission electron microscopy, and confocal Raman spectroscopy measurements to shed new light on the coupled effects of dimensionality, degree of intercalation, and intercalant order/disorder on the hard ferromagnetic behavior of FexTaS2. More generally, we show that chemical intercalation gives access to a rich synthetic parameter space for low-dimensional magnets, in which magnetic properties can be tailored by the choice of the host material and intercalant identity/amount, in addition to the manifold distinctive degrees of freedom available in atomically thin, van der Waals crystals