Quantum spin liquids.

Spin liquids are quantum phases of matter with a variety of unusual features arising from their topological character, including "fractionalization"-elementary excitations that behave as fractions of an electron. Although there is not yet universally accepted experimental evidence that establishes that any single material has a spin liquid ground state, in the past few years a number of materials have been shown to exhibit distinctive properties that are expected of a quantum spin liquid. Here, we review theoretical and experimental progress in this area.

Topological Magnon Bands in a Kagome Lattice Ferromagnet.

There is great interest in finding materials possessing quasiparticles with topological properties. Such materials may have novel excitations that exist on their boundaries which are protected against disorder. We report experimental evidence that magnons in an insulating kagome ferromagnet can have a topological band structure. Our neutron scattering measurements further reveal that one of the bands is flat due to the unique geometry of the kagome lattice. Spin wave calculations show that the measured band structure follows from a simple Heisenberg Hamiltonian with a Dzyaloshinkii-Moriya interaction. This serves as the first realization of an effectively two-dimensional topological magnon insulator--a new class of magnetic material that should display both a magnon Hall effect and protected chiral edge modes.

Dynamic scaling in the susceptibility of the spin-1/2 kagome lattice antiferromagnet herbertsmithite.

The spin-1/2 kagome lattice antiferromagnet herbertsmithite, ZnCu(3)(OH)(6)Cl(2), is a candidate material for a quantum spin liquid ground state. We show that the magnetic response of this material displays an unusual scaling relation in both the bulk ac susceptibility and the low energy dynamic susceptibility as measured by inelastic neutron scattering. The quantity chiT(alpha) with alpha approximately 0.66 can be expressed as a universal function of H/T or omega/T. This scaling is discussed in relation to similar behavior seen in systems influenced by disorder or by the proximity to a quantum critical point.

63Cu, 35Cl, and 1H NMR in the S=1/2 Kagome lattice ZnCu3(OH)6Cl2.

ZnCu(3)(OH)(6)Cl(2) (S=1/2) is a promising new candidate for an ideal Kagome Heisenberg antiferromagnet, because there is no magnetic phase transition down to approximately 50 mK. We investigated its local magnetic and lattice environments with NMR techniques. We demonstrate that the intrinsic local spin susceptibility decreases toward T=0, but that slow freezing of the lattice near approximately 50 K, presumably associated with OH bonds, contributes to a large increase of local spin susceptibility and its distribution. Spin dynamics near T=0 obey a power-law behavior in high magnetic fields.

Spin dynamics of the spin-1/2 kagome lattice antiferromagnet ZnCu3(OH)6Cl2.

We have performed thermodynamic and neutron scattering measurements on the S=1/2 kagomé lattice antiferromagnet ZnCu3(OH)6Cl2. The susceptibility indicates a Curie-Weiss temperature of theta CW approximately = -300 K; however, no magnetic order is observed down to 50 mK. Inelastic neutron scattering reveals a spectrum of low energy spin excitations with no observable gap down to 0.1 meV. The specific heat at low-T follows a power law temperature dependence. These results suggest that an unusual spin liquid state with essentially gapless excitations is realized in this kagomé lattice system.

Spin waves in the frustrated kagomé lattice antiferromagnet KFe3(OH)6(SO4)2.

The spin wave excitations of the S=5/2 kagomé lattice antiferromagnet KFe3(OH)6(SO4)2 have been measured using high-resolution inelastic neutron scattering. We directly observe a flat mode which corresponds to a lifted "zero energy mode," verifying a fundamental prediction for the kagomé lattice. A simple Heisenberg spin Hamiltonian provides an excellent fit to our spin wave data. The antisymmetric Dzyaloshinskii-Moriya interaction is the primary source of anisotropy and explains the low-temperature magnetization and spin structure.

Hydrogen produced from hydrohalic acid solutions by a two-electron mixed-valence photocatalyst.

Energy conversion cycles are aimed at driving unfavorable, small-molecule activation reactions with a photon harnessed by a transition metal complex. A challenge that has occupied researchers for several decades is to create molecular photocatalysts to promote the production of hydrogen from homogeneous solution. We now report the use of a two-electron mixed-valence dirhodium compound to photocatalyze the reduction of hydrohalic acid to hydrogen. In this cycle, photons break two RhII-X bonds of a LRh0-RhIIX2 core in the presence of a halogen trap to regenerate the active LRh0-Rh0 catalyst, which reacts with hydrohalic acid to produce hydrogen.

The whole story of the two-electron bond, with the delta bond as a paradigm.

It is shown that the delta bond, as found particularly in the Re(2)(6+) and Mo(2)(4+) cores of hundreds of compounds, provides a paradigm for the behavior of two-electron bonds of all types. By control of the angle of twist around the M-M axis, the strength of the bond can be systematically varied. By means of conventional electronic spectroscopy, nuclear magnetic resonance spectroscopy, and two-photon excitation spectroscopy, the entire picture of the manifold of four states for two electrons bonding two atoms, as first described by Coulson and Fischer in 1949, has been confirmed.

Xanthene-bridged cofacial bisporphyrins.

The synthesis and characterization of cofacial bisporphyrins juxtaposed by xanthene-bridged pillars are presented. The one-pot preparation of the xanthene dialdehyde avoids the lengthy bridge synthesis accompanying other cofacial porphyrin systems, thus allowing for the facile preparation of homobimetallic zinc (10), copper (11), and nickel (12) complexes. The cofacial orientation of the two porphyrin macrocycles was confirmed by X-ray crystallography. Structural data are provided for bisporphyrins 10-12: 10 (C79H82N8OZn2), triclinic, space group P1, a = 11.2671(2) A, b = 14.9809(2) A, c = 20.4852(2) A, alpha = 101.6680(10) degrees, beta = 100.8890(10) degrees, gamma = 101.8060(10) degrees, Z = 2; 11 (C79H82N8OCu2), triclinic, space group P1, a = 11.21410(10) A, b = 14.9539(5) A, c = 20.6915(7) A, alpha = 101.810(2) degrees, beta = 101.044(2) degrees, gamma = 101.722(2) degrees, Z = 2; 12 (C79H82N8ONi2), monoclinic, space group C2/c, a = 24.1671(4) A, b = 10.669 A, c = 50.5080(9) A, beta = 99.553(2) degrees, Z = 8. Exciton interactions between the porphyrin rings are apparent in electronic spectra, consistent with the cofacial superstructure. The combination of structural and spectroscopic data provides a basis for the design of additional metal derivatives for the activation of dioxygen and other small molecules.

Proton-coupled electron transfer.

Proton-coupled electron transfer (PCET) is an important mechanism for charge transfer in a wide variety of systems including biology- and materials-oriented venues. We review several areas where the transfer of an electron and proton is tightly coupled and discuss model systems that can provide an experimental basis for a test of PCET theory. In a PCET reaction, the electron and proton may transfer consecutively (ET/PT) or concertedly (ETPT). The distinction between these processes is formulated, and rate-constant expressions for the two reaction channels are presented. Methods for the evaluation of these rate constants are discussed that are based on dielectric continuum theory. Electron donor hydrogen-bonded-interface electron acceptor systems displaying PCET reactivity are presented, and the rate-constant expressions corresponding to the ETPT and ET/PT channels for several model reaction complexes are evaluated.

Direct spectroscopic detection of a zwitterionic excited state.

Two electrons in two weakly coupled orbitals give rise to two states (diradical) with electrons residing in separate orbitals and two states (zwitterionic) with both electrons paired in one orbital or the other. This two-electron, two-orbital state manifold has eluded experimental confirmation because the zwitterionic states have been difficult to locate. Two-photon excitation of fluorescence from Mo(2)CI(4)(PMe(3))(4) (D2d) has been measured with linearly and circularly polarized light. From the polarization ratio and the energy of the observed transition, the 2(1)A(1) (delta*delta*) excited state has been located and characterized. In conjunction with the one-photon allowed (1)B(2) (deltadelta*) excited state, the zwitterionic state manifold for the quadruply bonded metal-metal class of compounds is thus established.