Using Hyperoptimized Tensor Networks and First-Principles Electronic Structure to Simulate the Experimental Properties of the Giant {Mn84} Torus.

The single-molecule magnet {Mn84} is a challenge to theory because of its high nuclearity. We directly compute two experimentally accessible observables, the field-dependent magnetization up to 75 T and the temperature-dependent heat capacity, using parameter-free theory. In particular, we use first-principles calculations to derive short- and long-range exchange interactions and compute the exact partition function of the resulting classical Potts and Ising spin models for all 84 Mn S = 2 spins to obtain observables. The latter computation is made possible by using hyperoptimized tensor network contractions, a technique developed to simulate quantum supremacy circuits. We also synthesize the magnet and measure its heat capacity and magnetization, observing qualitative agreement between theory and experiment and identifying an unusual bump in the heat capacity and a plateau in the magnetization. Our work also identifies some limitations of current theoretical modeling in large magnets, such as sensitivity to small, long-range exchange couplings.

Theoretical prediction of magnetic exchange coupling constants from broken-symmetry coupled cluster calculations.

Exchange coupling constants (J) are fundamental to the understanding of spin spectra of magnetic systems. Here, we investigate the broken-symmetry (BS) approaches of Noodleman and Yamaguchi in conjunction with coupled cluster (CC) methods to obtain exchange couplings. J values calculated from CC in this fashion converge smoothly toward the full configuration interaction result with increasing level of CC excitation. We compare this BS-CC scheme to the complementary equation-of-motion CC approach on a selection of bridged molecular cases and give results from a few other methodologies for context.

Long-Range Ferromagnetic Exchange Interactions Mediated by Mn-CeIV-Mn Superexchange Involving Empty 4f Orbitals.

Reactions involving reductive aggregation of MnO4- in methanol in the presence of CeIV and an excess of carboxylic acid have led to the synthesis of structurally related Ce/Mn clusters, [Ce3Mn5O8(OMe)(O2CBut)13(MeOH)] (1) and [Ce2Mn3O5(O2CPh)9(MeOH)3] (2), containing at least one {Mn2Ce2O4} cubane unit. The cores of both clusters contain Mnx units separated by three (1) or two (2) CeIV ions. Fits of variable-temperature, solid-state dc and ac magnetic susceptibility data reveal dominant ferromagnetic interactions within 1 and 2, resulting in the maximum S = 17/2 and S = 5 ground state spins, respectively, and thus suggesting significant ferromagnetic (F) interactions between the Mnx units that are ≥6 Å apart and separated by four intervening bonds through diamagnetic CeIV. Fits of magnetic susceptibility data also revealed unusual long-range F interactions, and this finding was further supported by high-field EPR measurements and simulations. Density functional theory calculations and a Wannier function analysis confirm long-range interactions and indicate a Mn-Ce-Mn superexchange pathway via Mn-d/Ce-f orbital overlap/hybridization.

Three Jahn-Teller States of Matter in Spin-Crossover System Mn(taa).

Three high-spin phases recently discovered in the spin-crossover system Mn(taa) are identified through analysis by a combination of first-principles calculations and Monte Carlo simulation as a low-temperature Jahn-Teller ordered (solid) phase, an intermediate-temperature dynamically correlated (liquid) phase, and an uncorrelated (gas) phase. In particular, the Jahn-Teller liquid phase arises from competition between mixing with low-spin impurities, which drive the disorder, and intermolecular strain interactions. The latter are a key factor in both the spin-crossover phase transition and the magnetoelectric coupling. Jahn-Teller liquids may exist in other spin-crossover materials and materials that have multiple equivalent Jahn-Teller axes.

A gate defined quantum dot on the two-dimensional transition metal dichalcogenide semiconductor WSe2.

Two-dimensional layered materials, such as transition metal dichalcogenides (TMDCs), are promising materials for future electronics owing to their unique electronic properties. With the presence of a band gap, atomically thin gate defined quantum dots (QDs) can be achieved on TMDCs. Herein, standard semiconductor fabrication techniques are used to demonstrate quantum confined structures on WSe2 with tunnel barriers defined by electric fields, therefore eliminating the edge states induced by etching steps, which commonly appear in gapless graphene QDs. Over 40 consecutive Coulomb diamonds with a charging energy of approximately 2 meV were observed, showing the formation of a QD, which is consistent with the simulations. The size of the QD could be tuned over a factor of 2 by changing the voltages applied to the top gates. These results shed light on a way to obtain smaller quantum dots on TMDCs with the same top gate geometry compared to traditional GaAs/AlGaAs heterostructures with further research.