Conservation laws, radiative decay rates, and excited state localization in organometallic complexes with strong spin-orbit coupling

There is longstanding fundamental interest in 6-fold coordinated $d^6$ ($t_{2g}^6$) transition metal complexes such as [Ru(bpy)$_3$]$^{2+}$ and Ir(ppy)$_3$, particularly their phosphorescence. This interest has increased with the growing realisation that many of these complexes have potential uses in applications including photovoltaics, imaging, sensing, and light-emitting diodes. In order to design new complexes with properties tailored for specific applications a detailed understanding of the low-energy excited states, particularly the lowest energy triplet state, $T_1$, is required. Here we describe a model of pseudo-octahedral complexes based on a pseudo-angular momentum representation and show that the predictions of this model are in excellent agreement with experiment - even when the deviations from octahedral symmetry are large. This model gives a natural explanation of zero-field splitting of $T_1$ and of the relative radiative rates of the three sublevels in terms of the conservation of time-reversal parity and total angular momentum modulo two. We show that the broad parameter regime consistent with the experimental data implies significant localization of the excited state.Comment: 8 pages, 6 figs + sup info (20 pages, 19 figures - to view pdf download the source files

The origin of the difference in the superconducting critical temperatures of the beta_H and beta_L phases of (BEDT-TTF)_2I_3

Incommensurate lattice fluctuations are present in the beta_L phase (T_c = 1.5 K) of ET_2I_3 (where ET is BEDT-TTF - bis(ethylenedithio)tetrathiafulvalene) but are absent in the beta_H phase (T_c = 7 K). We propose that the disorder in the conformational degrees of freedom of the terminal ethylene groups of the ET molecules, which is required to stabilise the lattice fluctuations, increases the quasiparticle scattering rate and that this leads to the observed difference in the superconducting critical temperatures, T_c, of the two phases. We calculate the dependence of T_c on the interlayer residual resistivity. Our theory has no free parameters. Our predictions are shown to be consistent with experiment. We describe experiments to conclusively test our hypothesis.Comment: 4 pages, 1 figur

Spin-state ice in geometrically frustrated spin-crossover materials

Spin crossover materials contain metal ions that can access two spin-states: one low-spin (LS), the other high-spin (HS). We propose that frustrated elastic interactions can give rise to spin-state ices -- phases of matter without long-range order, characterized by a local constraint or `ice rule'. The low-energy physics of spin-state ices is described by an emergent divergence-less gauge field with a gap to topological excitations that are deconfined quasi-particles with spin fractionalized midway between the spins of the LS and HS states.Comment: Major edit, some new results; 8+2 page

Geometrical frustration in the spin liquid beta'-Me3EtSb[Pd(dmit)2]2 and the valence bond solid Me3EtP[Pd(dmit)2]2

We show that the electronic structures of the title compounds predicted by density functional theory (DFT) are well described by tight binding models. We determine the frustration ratio, J'/J, of the Heisenberg model on the anisotropic triangular lattice, which describes the spin degrees of freedom in the Mott insulating phase for a range of Pd(dmit)2 salts. All of the antiferromagnetic materials studied have J'/J 0.9, consistent with predictions for the Heisenberg model. All salts with 0.5 < J'/J < 0.9, where many-body theories find a number of competing ground states, are known, experimentally, to be charge ordered, valence bond solids or spin liquids.Comment: Accepted for publication in Phys. Rev. Lett. 4+11 pages, 3+15 figures, major rewrite, added calculations of Hubbard

Nuclear Magnetic Resonance in Low-Symmetry Superconductors

We consider the nuclear spin-lattice relaxation rate, $1/T_1T$ in superconductors with accidental nodes. We show that a Hebel-Slichter-like peak occurs even in the absence of an isotropic component of the superconducting gap. The logarithmic divergence found in clean, non-interacting models is controlled by both disorder and electron-electron interactions. However, for reasonable parameters, neither of these effects removes the peak altogether.Comment: 10 pages, 5 figure

Quantum frustration in organic Mott insulators: from spin liquids to unconventional superconductors

We review the interplay of frustration and strong electronic correlations in quasi-two-dimensional organic charge transfer salts, such as k-(BEDT-TTF)_2X and Et_nMe_{4-n}Pn[Pd(dmit)2]2. These two forces drive a range of exotic phases including spin liquids, valence bond crystals, pseudogapped metals, and unconventional superconductivity. Of particular interest is that in several materials there is a direct transition as a function of pressure from a spin liquid Mott insulating state to a superconducting state. Experiments on these materials raise a number of profound questions about the quantum behaviour of frustrated systems, particularly the intimate connection between spin liquids and superconductivity. Insights into these questions have come from a wide range of theoretical techniques including first principles electronic structure, quantum many-body theory and quantum field theory. In this review we introduce the basic ideas of the field by discussing a simple frustrated Heisenberg model with four spins. We then describe the key experimental results, emphasizing that for two materials, k-(BEDT-TTF)_2Cu_2(CN)_3 and EtMe_3Sb[Pd(dmit)_2]_2, there is strong evidence for a spin liquid ground state, and for EtMe_3P[Pd(dmit)_2]_2, a valence bond solid ground state. We review theoretical attempts to explain these phenomena, arguing that this can be captured by a Hubbard model on the anisotropic triangular lattice at half filling, and that resonating valence bond wavefunctions can capture most of the essential physics. We review evidence that this model can have a spin liquid ground state for a range of parameters that are realistic for the relevant materials. We conclude by summarising the progress made thus far and identifying some of the key questions still to be answered.Comment: Major rewrite. New material added and many typos corrected. 67 pages, 41 figures. Thanks to those who commented on the previous versio

Symmetry of the superconducting order parameter in frustrated systems determined by the spatial anisotropy of spin correlations

We study the resonating valence bond (RVB) theory of the Hubbard-Heisenberg model on the half-filled anisotropic triangular lattice. Varying the frustration changes the wavevector of maximum spin correlation in the Mott insulating phase. This, in turn, changes the symmetry of the superconducting state, that occurs at the boundary of the Mott insulating phase. We propose that this physics is realised in several families of quasi-two-dimensional organic superconductors.Comment: To appear in Phys. Rev. Lett. - 5 pages, 4 fig

Space infrared telescope pointing control system. Infrared telescope tracking in the presence of target motion

The use of charge-coupled-devices, or CCD's, has been documented by a number of sources as an effective means of providing a measurement of spacecraft attitude with respect to the stars. A method exists of defocussing and interpolation of the resulting shape of a star image over a small subsection of a large CCD array. This yields an increase in the accuracy of the device by better than an order of magnitude over the case when the star image is focussed upon a single CCD pixel. This research examines the effect that image motion has upon the overall precision of this star sensor when applied to an orbiting infrared observatory. While CCD's collect energy within the visible spectrum of light, the targets of scientific interest may well have no appreciable visible emissions. Image motion has the effect of smearing the image of the star in the direction of motion during a particular sampling interval. The presence of image motion is incorporated into a Kalman filter for the system, and it is shown that the addition of a gyro command term is adequate to compensate for the effect of image motion in the measurement. The updated gyro model is included in this analysis, but has natural frequencies faster than the projected star tracker sample rate for dim stars. The system state equations are reduced by modelling gyro drift as a white noise process. There exists a tradeoff in selected star tracker sample time between the CCD, which has improved noise characteristics as sample time increases, and the gyro, which will potentially drift further between long attitude updates. A sample time which minimizes pointing estimation error exists for the random drift gyro model as well as for a random walk gyro model