Density-functional theory may be used to predict both the frequency and the dipole moment of the fundamental oscillations of molecular crystals. Suitably polarized photons at those frequencies excite such oscillations. Thus, in principle, terahertz spectroscopy may confirm the calculated fundamental modes of amino acids. However, reports to date have multiple shortcomings: (a) material of uncertain purity and morphology and diluted in a binder material is employed; (b) consequently, vibrations along all crystal axes are excited simultaneously; (c) data are restricted to room temperature, where resonances are broad and the background dominant; and (d) comparison with theory has been unsatisfactory (in part because the theory assumes zero temperature). Here, we overcome all four obstacles, in reporting detailed low-temperature polarized THz spectra of single-crystal l-alanine, assigning vibrational modes using density-functional theory, and comparing the calculated dipole moment vector direction to the electric field polarization of the measured spectra. Our direct and detailed comparison of theory with experiment corrects previous mode assignments for l-alanine, and reveals unreported modes, previously obscured by closely spaced spectral absorptions. The fundamental modes are thereby determined.
Terahertz Spectroscopy , Terahertz Spectroscopy/methods , Density Functional Theory , Vibration , Alanine/chemistry , Amino Acids
We present a combined experimental and theoretical study of the mineral atacamite Cu_{2}Cl(OH)_{3}. Density-functional theory yields a Hamiltonian describing anisotropic sawtooth chains with weak 3D connections. Experimentally, we fully characterize the antiferromagnetically ordered state. Magnetic order shows a complex evolution with the magnetic field, while, starting at 31.5 T, we observe a plateaulike magnetization at about M_{sat}/2. Based on complementary theoretical approaches, we show that the latter is unrelated to the known magnetization plateau of a sawtooth chain. Instead, we provide evidence that the magnetization process in atacamite is a field-driven canting of a 3D network of weakly coupled sawtooth chains that form giant moments.
Recently a new one-dimensional (1D) quantum spin chain system has been reported: catena-dichloro(2-Cl-3Mpy)copper(II), (where 2-Cl-3Mpy=2-chloro-3-methylpyridine). Preliminary calculations and bulk magnetic property measurements indicate that this system does not undergo magnetic ordering down to 1.8 K and is a prime candidate for investigating frustration in a J 1/J 2 system (where the nearest neighbour interactions, J 1, are ferromagnetic and the next nearest neighbour interactions, J 2, are antiferromagnetic). Calculations predicted three possible magnetic interaction strengths for J 1 below 6 meV depending on the orientation of the ligand. For one of the predicted J 1 values, the existence of a quantum critical point is implied. A deuterated sample of catena-dichloro(2-Cl-3Mpy)copper(II) was synthesised and the excitations measured using inelastic neutron scattering. Scattering indicated the most likely scenario involves spin-chains where each chain consists of only one of the three possible magnetic excitations in this material, rather than the completely random array of exchange interactions within each chain as predicted by Herringer et al (2014 Chem. Eur. J. 20 8355-62). This indicates the possibility of tuning the chemical structure to favour a system which may exhibit a quantum critical point.
Low-temperature neutron diffraction and NMR studies of field-induced phases in linarite are presented for magnetic fields Hâ¥b axis. A two-step spin-flop transition is observed, as well as a transition transforming a helical magnetic ground state into an unusual magnetic phase with sine-wave-modulated moments â¥H. An effective J[over Ë]_{1}-J[over Ë]_{2} single-chain model with a magnetization-dependent frustration ratio α_{eff}=-J[over Ë]_{2}/J[over Ë]_{1} is proposed. The latter is governed by skew interchain couplings and shifted to the vicinity of the ferromagnetic critical point. It explains qualitatively the observation of a rich variety of exotic longitudinal collinear spin-density wave, SDW_{p}, states (9≥p≥2).
We study the strongly anisotropic quasi-one-dimensional S = 1 quantum magnet NiCl2·4SC(NH2)2 using elastic and inelastic neutron scattering. We demonstrate that a magnetic field splits the excited doublet state and drives the lower doublet state to zero energy at a critical field Hc1. For Hc1 < H < Hc2, where Hc2 indicates the transition to a fully magnetized state, three-dimensional magnetic order is established with the AF moment perpendicular to the magnetic field. We mapped the temperature/magnetic field phase diagram, and we find that the total ordered magnetic moment reaches m(tot) = 2.1 µB at the field µ(0)H = 6 T and is thus close to the saturation value of the fully ordered moment. We study the magnetic spin dynamics in the fully magnetized state for H > Hc2, and we demonstrate the presence of an AF interaction between Ni(2+) on the two interpenetrating sublattices. In the antiferromagnetically ordered phase, the spin-waves that develop from the lower-energy doublet are split into two modes. This is most likely the result of the presence of the AF interaction between the interpenetrating lattices.
Neutron scattering in strong magnetic fields is used to show the spin resonance in superconducting CeCoIn(5) (T(c)=2.3 K) is a doublet. The underdamped resonance (hΓ=0.069±0.019 meV) Zeeman splits into two modes at E(±)=hΩ(0)±αµ(B)µ(0)H with α=0.96±0.05. A linear extrapolation of the lower peak reaches zero energy at 11.2±0.5 T, near the critical field for the incommensurate "Q phase." Kenzelmann et al. [Science 321, 1652 (2008)] This, taken with the integrated weight and polarization of the low-energy mode (E(-)), indicates that the Q phase can be interpreted as a Bose condensate of spin excitons.
In this Letter, we explore the phase diagram and excitations of a distorted triangular lattice antiferromagnet. The unique two-dimensional distortion considered here is very different from the "isosceles"-type distortion that has been extensively investigated. We show that it is able to stabilize a 120° spin structure for a large range of exchange interaction values, while new structures are found for extreme distortions. A physical realization of this model is α-CaCr(2)O(4), which has a 120° structure but lies very close to the phase boundary. This is verified by inelastic neutron scattering which reveals unusual rotonlike minima at reciprocal space points different from those corresponding to the magnetic order.
It is widely believed that magnetic excitations become increasingly incoherent as the temperature is raised due to random collisions which limit their lifetime. This picture is based on spin-wave calculations for gapless magnets in 2 and 3 dimensions and is observed experimentally as a symmetric Lorentzian broadening in energy. Here, we investigate a three-dimensional dimer antiferromagnet and find unexpectedly that the broadening is asymmetric-indicating that far from thermal decoherence, the excitations behave collectively like a strongly correlated gas. This result suggests that a temperature activated coherent state of quasiparticles is not confined to special cases like the highly dimerized spin-1/2 chain but is found generally in dimerized antiferromagnets of all dimensionalities and perhaps gapped magnets in general.
The spin waves in a powdered sample of a quasi-two-dimensional antiferromagnet, FePS(3), have been measured using neutron inelastic scattering. The data could be modelled and the exchange interactions determined using a two-dimensional Heisenberg Hamiltonian with single ion anisotropy. A suitable fit to the data could only be achieved by including magnetic interactions up to the third nearest neighbour, which is consistent with the findings for other members of the MPS(3) family (M=transition metal). The best fit parameters at 6 K were J(1) = 1.49 meV, J(2) = 0.04 meV, J(3) =- 0.6 meV, with an anisotropy of Δ = 3.7 meV. Measurements as a function of temperature give a coarse measure of the behaviour of the anisotropy and the nature of the phase transition.
We present a combined neutron diffraction and bulk thermodynamic study of the natural mineral linarite PbCuSO4(OH)2, this way establishing the nature of the ground-state magnetic order. An incommensurate magnetic ordering with a propagation vector k=(0,0.186,1/2) was found below T(N)=2.8 K in a zero magnetic field. The analysis of the neutron diffraction data yields an elliptical helical structure, where one component (0.638µ(B)) is in the monoclinic ac plane forming an angle with the a axis of 27(2)°, while the other component (0.833µ(B)) points along the b axis. From a detailed thermodynamic study of bulk linarite in magnetic fields up to 12 T, applied along the chain direction, a very rich magnetic phase diagram is established, with multiple field-induced phases, and possibly short-range-order effects occurring in high fields. Our data establish linarite as a model compound of the frustrated one-dimensional spin chain, with ferromagnetic nearest-neighbor and antiferromagnetic next-nearest-neighbor interactions. Long-range magnetic order is brought about by interchain coupling 1 order of magnitude smaller than the intrachain coupling.
The magnetic properties of Ho(2)Sn(2)O(7) have been investigated and compared to other spin ice compounds. Although the lattice has expanded by 3% relative to the better studied Ho(2)Ti(2)O(7) spin ice, no significant changes were observed in the high temperature properties, T is more or approximately equal to 20 K. As the temperature is lowered and correlations develop, Ho(2)Sn(2)O(7) enters its quantum phase at a slightly higher temperature than Ho(2)Ti(2)O(7) and is more antiferromagnetic in character. Below 80 K a weak inelastic mode associated with the holmium nuclear spin system has been measured. The hyperfine field at the holmium nucleus was found to be ≈700 T.
We report neutron scattering measurements of critical magnetic excitations in the weakly ferromagnetic superconductor UCoGe. The strong non-Landau damping of the excitations we observe, although unusual, has been found in another related ferromagnet, UGe(2) at zero pressure. However, we also find that there is a significant anisotropy of the magnetic correlation length in UCoGe that contrasts with an almost isotropic length for UGe(2). The values of the magnetic correlation length and damping are found to be compatible with superconductivity on small Fermi-surface pockets. The anisotropy may be important to explain why UCoGe is a superconductor at zero pressure while UGe(2) is not.
Sources of magnetic fields-magnetic monopoles-have so far proven elusive as elementary particles. Condensed-matter physicists have recently proposed several scenarios of emergent quasiparticles resembling monopoles. A particularly simple proposition pertains to spin ice on the highly frustrated pyrochlore lattice. The spin-ice state is argued to be well described by networks of aligned dipoles resembling solenoidal tubes-classical, and observable, versions of a Dirac string. Where these tubes end, the resulting defects look like magnetic monopoles. We demonstrated, by diffuse neutron scattering, the presence of such strings in the spin ice dysprosium titanate (Dy2Ti2O7). This is achieved by applying a symmetry-breaking magnetic field with which we can manipulate the density and orientation of the strings. In turn, heat capacity is described by a gas of magnetic monopoles interacting via a magnetic Coulomb interaction.
By using bulk magnetization, electron spin resonance (ESR), heat capacity, and neutron scattering techniques, we characterize the thermodynamic and quantum phase diagrams of Ba3Cr2O8. Our ESR measurements indicate that the low field paramagnetic ground state is a mixed state of the singlet and the Sz=0 triplet for H perpendicular c. This suggests the presence of an intradimer Dzyaloshinsky-Moriya (DM) interaction with a DM vector perpendicular to the c axis.
The quasi-two-dimensional antiferromagnet FePS(3) has been investigated using inelastic neutron spectroscopy with the time-of-flight spectrometer HET at the ISIS spallation neutron source. In the paramagnetic regime, two clearly resolved, high energy excitations were observed in the low scattering angle detector banks at 195(5) meV and 430(10) meV. The absence of these transitions from the high angle detector banks indicates that they are likely to be due to the crystal fields and magnetic in origin. The two transitions most probably represent electronic transitions in the Fe(2+) ion among the low lying crystal field and spin-orbit split levels raised from the ground state. It has not yet been determined why the energies are greater than those observed in a comparable Raman experiment.
Neutron scattering measurements have been performed on polycrystalline Tb(2)Sn(2)O(7) at temperatures above and below that of the phase transition, T(N) = 0.87 K, to investigate further the spin dynamics in the magnetically ordered state. In particular, new neutron spin echo results are presented showing a dependence on Q in the dynamics. We show evidence of the coexistence of static ferromagnetism and dynamically fluctuating spins down to 30 mK and we make a comparison of this partially ordered system to the spin liquid Tb(2)Ti(2)O(7).
We present a specific heat and inelastic neutron scattering study in magnetic fields up into the 1/3 magnetization plateau phase of the diamond chain compound azurite Cu3(CO3)2(OH)2. We establish that the magnetization plateau is a dimer-monomer state, i.e., consisting of a chain of S=1/2 monomers, which are separated by S=0 dimers on the diamond chain backbone. The effective spin couplings Jmono/kB=10.1(2) K and Jdimer/kB=1.8(1) K are derived from the monomer and dimer dispersions. They are associated to microscopic couplings J1/kB=1(2) K, J2/kB=55(5) K and a ferromagnetic J3/kB=-20(5) K, possibly as result of dz2} orbitals in the Cu-O bonds providing superexchange (SE) pathways with JSE=6.5 K.
High-resolution x-ray scattering measurements on single crystal Tb2Ti2O7 reveal finite structural correlations at low temperatures. This geometrically frustrated pyrochlore is known to exhibit a spin-liquid or cooperative paramagnetic state at temperatures below approximately 20 K. Parametric studies of structural Bragg peaks appropriate to the Fd3[over ]m space group of Tb2Ti2O7 reveal substantial broadening and peak intensity reduction in the temperature regime 20 K to 300 mK. We also observe a small, anomalous lattice expansion on cooling below a density maximum at approximately 18 K. These measurements are consistent with the development of fluctuations above a cooperative Jahn-Teller, cubic-tetragonal phase transition at very low temperatures.
High resolution time-of-flight neutron scattering measurements on Tb(2)Ti(2)0(7) reveal a rich low temperature phase diagram in the presence of a magnetic field applied along [110]. In zero field at T = 0.4 K, Tb(2)Ti(2)0(7) is a highly correlated cooperative paramagnet with disordered spins residing on a pyrochlore lattice of corner-sharing tetrahedra. Application of a small field condenses much of the magnetic diffuse scattering, characteristic of the disordered spins, into a new Bragg peak characteristic of a polarized paramagnet. At higher fields, a magnetically ordered phase is induced, which supports spin wave excitations indicative of continuous, rather than Ising-like, spin degrees of freedom.
