Publications


La2SrCr2O7: Controlling the Tilting Distortions of n = 2 Ruddlesden-Popper Phases through A-Site Cation Order.

Inorganic chemistry 55 (2016) 8951-8960

R Zhang, BM Abbett, G Read, F Lang, T Lancaster, TT Tran, PS Halasyamani, SJ Blundell, NA Benedek, MA Hayward

Structural characterization by neutron diffraction, supported by magnetic, SHG, and μ(+)SR data, reveals that the n = 2 Ruddlesden-Popper phase La2SrCr2O7 adopts a highly unusual structural configuration in which the cooperative rotations of the CrO6 octahedra are out of phase in all three Cartesian directions (ΦΦΦz/ΦΦΦz; a(-)a(-)c(-)/a(-)a(-)c(-)) as described in space group A2/a. First-principles DFT calculations indicate that this unusual structural arrangement can be attributed to coupling between the La/Sr A-site distribution and the rotations of the CrO6 units, which combine to relieve the local deformations of the chromium-oxygen octahedra. This coupling suggests new chemical "handles" by which the rotational distortions or A-site cation order of Ruddlesden-Popper phases can be directed to optimize physical behavior. Low-temperature neutron diffraction data and μ(+)SR data indicate La2SrCr2O7 adopts a G-type antiferromagnetically ordered state below TN ∼ 260 K.


Making hybrid [n]-rotaxanes as supramolecular arrays of molecular electron spin qubits.

Nature communications 7 (2016) 10240-

A Fernandez, J Ferrando-Soria, EM Pineda, F Tuna, IJ Vitorica-Yrezabal, C Knappke, J Ujma, CA Muryn, GA Timco, PE Barran, A Ardavan, REP Winpenny

Quantum information processing (QIP) would require that the individual units involved--qubits--communicate to other qubits while retaining their identity. In many ways this resembles the way supramolecular chemistry brings together individual molecules into interlocked structures, where the assembly has one identity but where the individual components are still recognizable. Here a fully modular supramolecular strategy has been to link hybrid organic-inorganic [2]- and [3]-rotaxanes into still larger [4]-, [5]- and [7]-rotaxanes. The ring components are heterometallic octanuclear [Cr7NiF8(O2C(t)Bu)16](-) coordination cages and the thread components template the formation of the ring about the organic axle, and are further functionalized to act as a ligand, which leads to large supramolecular arrays of these heterometallic rings. As the rings have been proposed as qubits for QIP, the strategy provides a possible route towards scalable molecular electron spin devices for QIP. Double electron-electron resonance experiments demonstrate inter-qubit interactions suitable for mediating two-qubit quantum logic gates.


Robustness of superconductivity to competing magnetic phases in tetragonal FeS

PHYSICAL REVIEW B 94 (2016) ARTN 134509

FKK Kirschner, F Lang, CV Topping, PJ Baker, FL Pratt, SE Wright, DN Woodruff, SJ Clarke, SJ Blundell


Fourier space derivation of the demagnetization tensor for uniformly magnetized objects of cylindrical symmetry

JOURNAL OF MAGNETISM AND MAGNETIC MATERIALS 401 (2016) 1060-1067

F Lang, SJ Blundell


Quantum Interference in Graphene Nanoconstrictions.

Nano letters 16 (2016) 4210-4216

P Gehring, H Sadeghi, S Sangtarash, CS Lau, J Liu, A Ardavan, JH Warner, CJ Lambert, GAD Briggs, JA Mol

We report quantum interference effects in the electrical conductance of chemical vapor deposited graphene nanoconstrictions fabricated using feedback controlled electroburning. The observed multimode Fabry-Pérot interferences can be attributed to reflections at potential steps inside the channel. Sharp antiresonance features with a Fano line shape are observed. Theoretical modeling reveals that these Fano resonances are due to localized states inside the constriction, which couple to the delocalized states that also give rise to the Fabry-Pérot interference patterns. This study provides new insight into the interplay between two fundamental forms of quantum interference in graphene nanoconstrictions.


The Parent Li(OH)FeSe Phase of Lithium Iron Hydroxide Selenide Superconductors.

Inorganic chemistry 55 (2016) 9886-9891

DN Woodruff, F Schild, CV Topping, SJ Cassidy, JN Blandy, SJ Blundell, AL Thompson, SJ Clarke

Lithiation of hydrothermally synthesized Li1-xFex(OH)Fe1-ySe turns on high-temperature superconductivity when iron ions are displaced from the hydroxide layers by reductive lithiation to fill the vacancies in the iron selenide layers. Further lithiation results in reductive iron extrusion from the hydroxide layers, which turns off superconductivity again as the stoichiometric composition Li(OH)FeSe is approached. The results demonstrate the twin requirements of stoichiometric FeSe layers and reduction of Fe below the +2 oxidation state as found in several iron selenide superconductors.


Magnetic phase diagram of La2−xSrxCoO4 revised using muon-spin relaxation

Physical Review B - Condensed Matter and Materials Physics American Physical Society (2016)

RC Williams, F Xiao, T Lancaster, R De Renzi, G Allodi, S Bordignon, PG Freeman, FL Pratt, SR Giblin, JS Moeller, SJ Blundell, AT Boothroyd, D Prabhakaran


Studies of a Large Odd-Numbered Odd-Electron Metal Ring: Inelastic Neutron Scattering and Muon Spin Relaxation Spectroscopy of Cr8 Mn.

Chemistry (Weinheim an der Bergstrasse, Germany) 22 (2016) 1779-1788

ML Baker, T Lancaster, A Chiesa, G Amoretti, PJ Baker, C Barker, SJ Blundell, S Carretta, D Collison, HU Güdel, T Guidi, EJL McInnes, JS Möller, H Mutka, J Ollivier, FL Pratt, P Santini, F Tuna, PLW Tregenna-Piggott, IJ Vitorica-Yrezabal, GA Timco, REP Winpenny

The spin dynamics of Cr8 Mn, a nine-membered antiferromagnetic (AF) molecular nanomagnet, are investigated. Cr8 Mn is a rare example of a large odd-membered AF ring, and has an odd-number of 3d-electrons present. Odd-membered AF rings are unusual and of interest due to the presence of competing exchange interactions that result in frustrated-spin ground states. The chemical synthesis and structures of two Cr8 Mn variants that differ only in their crystal packing are reported. Evidence of spin frustration is investigated by inelastic neutron scattering (INS) and muon spin relaxation spectroscopy (μSR). From INS studies we accurately determine an appropriate microscopic spin Hamiltonian and we show that μSR is sensitive to the ground-spin-state crossing from S=1/2 to S=3/2 in Cr8 Mn. The estimated width of the muon asymmetry resonance is consistent with the presence of an avoided crossing. The investigation of the internal spin structure of the ground state, through the analysis of spin-pair correlations and scalar-spin chirality, shows a non-collinear spin structure that fluctuates between non-planar states of opposite chiralities.


Experimental and Theoretical Electron Density Analysis of Copper Pyrazine Nitrate Quasi-Low-Dimensional Quantum Magnets.

Journal of the American Chemical Society 138 (2016) 2280-2291

LHR Dos Santos, A Lanza, AM Barton, J Brambleby, WJA Blackmore, PA Goddard, F Xiao, RC Williams, T Lancaster, FL Pratt, SJ Blundell, J Singleton, JL Manson, P Macchi

The accurate electron density distribution and magnetic properties of two metal-organic polymeric magnets, the quasi-one-dimensional (1D) Cu(pyz)(NO3)2 and the quasi-two-dimensional (2D) [Cu(pyz)2(NO3)]NO3·H2O, have been investigated by high-resolution single-crystal X-ray diffraction and density functional theory calculations on the whole periodic systems and on selected fragments. Topological analyses, based on quantum theory of atoms in molecules, enabled the characterization of possible magnetic exchange pathways and the establishment of relationships between the electron (charge and spin) densities and the exchange-coupling constants. In both compounds, the experimentally observed antiferromagnetic coupling can be quantitatively explained by the Cu-Cu superexchange pathway mediated by the pyrazine bridging ligands, via a σ-type interaction. From topological analyses of experimental charge-density data, we show for the first time that the pyrazine tilt angle does not play a role in determining the strength of the magnetic interaction. Taken in combination with molecular orbital analysis and spin density calculations, we find a synergistic relationship between spin delocalization and spin polarization mechanisms and that both determine the bulk magnetic behavior of these Cu(II)-pyz coordination polymers.


Muon-spin relaxation study of the double perovskite insulators Sr2 BOsO6 (B  =  Fe, Y, ln).

Journal of physics. Condensed matter : an Institute of Physics journal 28 (2016) 076001-

RC Williams, F Xiao, IO Thomas, SJ Clark, T Lancaster, GA Cornish, SJ Blundell, W Hayes, AK Paul, C Felser, M Jansen

We present the results of zero-field muon-spin relaxation measurements made on the double perovskite insulators Sr2 BOsO6 (B = Fe,Y, In). Spontaneous muon-spin precession indicative of quasistatic long range magnetic ordering is observed in Sr2FeOsO6 within the AF1 antiferromagnetic phase for temperatures below [Formula: see text] K. Upon cooling below T2≈67 K the oscillations cease to be resolvable owing to the coexistence of the AF1 and AF2 phases, which leads to a broader range of internal magnetic fields. Using density functional calculations we identify a candidate muon stopping site within the unit cell, which dipole field simulations show to be consistent with the proposed magnetic structure. The possibility of incommensurate magnetic ordering is discussed for temperatures below TN = 53 K and 25 K for Sr2YOsO6 and Sr2InOsO6, respectively.


Commensurate 4a0-period charge density modulations throughout the Bi<inf>2</inf>Sr<inf>2</inf>CaCu<inf>2</inf>O<inf>8+x</inf>pseudogap regime

Proceedings of the National Academy of Sciences of the United States of America 113 (2016) 12661-12666

A Mesaros, K Fujita, SD Edkins, MH Hamidian, H Eisaki, SI Uchida, JCS Davis, MJ Lawler, EA Kim

Theories based upon strong real space (r-space) electron-electron interactions have long predicted that unidirectional charge density modulations (CDMs) with four-unit-cell (4a0) periodicity should occur in the hole-doped cuprate Mott insulator (MI). Experimentally, however, increasing the hole density p is reported to cause the conventionally defined wavevector QA of the CDM to evolve continuously as if driven primarily by momentum-space (k-space) effects. Here we introduce phase-resolved electronic structure visualization for determination of the cuprate CDM wavevector. Remarkably, this technique reveals a virtually doping-independent locking of the local CDM wavevector at, Q0,=2π=4a0throughout the underdoped phase diagram of the canonical cuprate Bi2Sr2CaCu2O8. These observations have significant fundamental consequences because they are orthogonal to a k-space (Fermi-surface)-based picture of the cuprate CDMs but are consistent with strong-coupling r-space-based theories. Our findings imply that it is the latter that provides the intrinsic organizational principle for the cuprate CDM state.


Detection of a Cooper-pair density wave in Bi<inf>2</inf>Sr<inf>2</inf>CaCu<inf>2</inf>O<inf>8+x</inf>

Nature 532 (2016) 343-347

MH Hamidian, SD Edkins, SH Joo, A Kostin, H Eisaki, S Uchida, MJ Lawler, EA Kim, AP Mackenzie, K Fujita, J Lee, JCS Davis

© 2016 Macmillan Publishers Limited. All rights reserved. The quantum condensate of Cooper pairs forming a superconductor was originally conceived as being translationally invariant. In theory, however, pairs can exist with finite momentum Q, thus generating a state with a spatially modulated Cooper-pair density. Such a state has been created in ultracold 6 Li gas but never observed directly in any superconductor. It is now widely hypothesized that the pseudogap phase of the copper oxide superconductors contains such a 'pair density wave' state. Here we report the use of nanometre-resolution scanned Josephson tunnelling microscopy to image Cooper pair tunnelling from a d-wave superconducting microscope tip to the condensate of the superconductor Bi2Sr2CaCu2O8+x. We demonstrate condensate visualization capabilities directly by using the Cooper-pair density variations surrounding zinc impurity atoms and at the Bi2Sr2CaCu2O8+x crystal supermodulation. Then, by using Fourier analysis of scanned Josephson tunnelling images, we discover the direct signature of a Cooper-pair density modulation at wavevectors QP ≈ (0.25, 0)2π/a0 and (0, 0.25)2π/a0 in Bi2Sr2CaCu2O8+x. The amplitude of these modulations is about five per cent of the background condensate density and their form factor exhibits primarily s or s′ symmetry. This phenomenology is consistent with Ginzburg-Landau theory when a charge density wave with d-symmetry form factor and wavevector QC = QP coexists with a d-symmetry superconductor; it is also predicted by several contemporary microscopic theories for the pseudogap phase.


Atomic-scale electronic structure of the cuprate d-symmetry form factor density wave state

Nature Physics 12 (2016) 150-156

MH Hamidian, SD Edkins, CK Kim, JC Davis, AP Mackenzie, H Eisaki, S Uchida, MJ Lawler, EA Kim, S Sachdev, K Fujita

© 2016 Macmillan Publishers Limited. Research on high-temperature superconducting cuprates is at present focused on identifying the relationship between the classic 'pseudogap'phenomenon and the more recently investigated density wave state. This state is generally characterized by a wavevector Q parallel to the planar Cu-O-Cu bonds along with a predominantly d-symmetry form factor (dFF-DW). To identify the microscopic mechanism giving rise to this state, one must identify the momentum-space states contributing to the dFF-DW spectral weight, determine their particle-hole phase relationship about the Fermi energy, establish whether they exhibit a characteristic energy gap, and understand the evolution of all these phenomena throughout the phase diagram. Here we use energy-resolved sublattice visualization of electronic structure and reveal that the characteristic energy of the dFF-DW modulations is actually the 'pseudogap' energy Δ1. Moreover, we demonstrate that the dFF-DW modulations at E=-Δ1 (filled states) occur with relative phase φ compared to those at E=Δ1 (empty states). Finally, we show that the conventionally defined dFF-DW Q corresponds to scattering between the 'hot frontier'regions of momentum-space beyond which Bogoliubov quasiparticles cease to exist. These data indicate that the cuprate dFF-DW state involves particle-hole interactions focused at the pseudogap energy scale and between the four pairs of 'hot frontier'regions in momentum space where the pseudogap opens.


Bimetallic MOFs (H3O)x[Cu(MF6)(pyrazine)2]·(4 - x)H2O (M = V4+, x = 0; M = Ga3+, x = 1): co-existence of ordered and disordered quantum spins in the V4+ system.

Chemical communications (Cambridge, England) 52 (2016) 12653-12656

JL Manson, JA Schlueter, KE Garrett, PA Goddard, T Lancaster, JS Möller, SJ Blundell, AJ Steele, I Franke, FL Pratt, J Singleton, J Bendix, SH Lapidus, M Uhlarz, O Ayala-Valenzuela, RD McDonald, M Gurak, C Baines

The title compounds are bimetallic MOFs containing [Cu(pyz)2]2+ square lattices linked by MF6n- octahedra. In each, only the Cu2+ spins exhibit long-range magnetic order below 3.5 K (M = V4+) and 2.6 K (M = Ga3+). The V4+ spins remain disordered down to 0.5 K.


La2SrCr2O7F2: A Ruddlesden-Popper Oxyfluoride Containing Octahedrally Coordinated Cr(4+) Centers.

Inorganic chemistry 55 (2016) 3169-3174

R Zhang, G Read, F Lang, T Lancaster, SJ Blundell, MA Hayward

The low-temperature fluorination of the n = 2 Ruddlesden-Popper phase La2SrCr2O7 yields La2SrCr2O7F2 via a topochemical fluorine insertion reaction. The structure-conserving nature of the fluorination reaction means that the chromium centers of the initial oxide phase retain an octahedral coordination environment in the fluorinated product, resulting in a material containing an extended array of apex-linked Cr(4+)O6 units. Typically materials containing networks of octahedrally coordinated Cr(4+) centers can only be prepared at high pressure; thus, the preparation of La2SrCr2O7F2 demonstrates that low-temperature topochemical reactions offer an alternative synthesis route to materials of this type. Neutron diffraction, magnetization, and μ(+)SR data indicate that La2SrCr2O7F2 undergoes a transition to an antiferromagnetic state below TN ≈ 140 K. The structure-property relations of this phase and other Cr(4+) oxide phases are discussed.


Unconventional magnetism on a honeycomb lattice in alpha-RuCl3 studied by muon spin rotation

PHYSICAL REVIEW B 94 (2016) ARTN 020407

F Lang, PJ Baker, AA Haghighirad, Y Li, D Prabhakaran, R Valenti, SJ Blundell


Ordering Gold Nanoparticles with DNA Origami Nanoflowers.

ACS nano 10 (2016) 7303-7306

R Schreiber, I Santiago, A Ardavan, AJ Turberfield

Nanostructured materials, including plasmonic metamaterials made from gold and silver nanoparticles, provide access to new materials properties. The assembly of nanoparticles into extended arrays can be controlled through surface functionalization and the use of increasingly sophisticated linkers. We present a versatile way to control the bonding symmetry of gold nanoparticles by wrapping them in flower-shaped DNA origami structures. These "nanoflowers" assemble into two-dimensonal gold nanoparticle lattices with symmetries that can be controlled through auxiliary DNA linker strands. Nanoflower lattices are true composites: interactions between the gold nanoparticles are mediated entirely by DNA, and the DNA origami will fold into its designed form only in the presence of the gold nanoparticles.


Transverse field muon-spin rotation measurement of the topological anomaly in a thin film of MnSi

PHYSICAL REVIEW B 93 (2016) ARTN 140412

T Lancaster, F Xiao, Z Salman, IO Thomas, SJ Blundell, FL Pratt, SJ Clark, T Prokscha, A Suter, SL Zhang, AA Baker, T Hesjedal


Nanoscale depth-resolved polymer dynamics probed by the implantation of low energy muons

POLYMER 105 (2016) 516-525

FL Pratt, T Lancaster, PJ Baker, SJ Blundell, T Prokscha, E Morenzoni, A Suter, HE Assender


Anisotropic local modification of crystal field levels in Pr-based pyrochlores: a muon-induced effect modeled using density functional theory.

Physical review letters 114 (2015) 017602-

FR Foronda, F Lang, JS Möller, T Lancaster, AT Boothroyd, FL Pratt, SR Giblin, D Prabhakaran, SJ Blundell

Although muon spin relaxation is commonly used to probe local magnetic order, spin freezing, and spin dynamics, we identify an experimental situation in which the measured response is dominated by an effect resulting from the muon-induced local distortion rather than the intrinsic behavior of the host compound. We demonstrate this effect in some quantum spin ice candidate materials Pr(2)B(2)O(7) (B=Sn, Zr, Hf), where we detect a static distribution of magnetic moments that appears to grow on cooling. Using density functional theory we show how this effect can be explained via a hyperfine enhancement arising from a splitting of the non-Kramers doublet ground states on Pr ions close to the muon, which itself causes a highly anisotropic distortion field. We provide a quantitative relationship between this effect and the measured temperature dependence of the muon relaxation and discuss the relevance of these observations to muon experiments in other magnetic materials.

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