Decoherence window and electron-nuclear cross-relaxation in the molecular magnet V 15

Rabi oscillations in the V_15 Single Molecule Magnet (SMM) embedded in the surfactant DODA have been studied at different microwave powers. An intense damping peak is observed when the Rabi frequency Omega_R falls in the vicinity of the Larmor frequency of protons w_N, while the damping time t_R of oscillations reaches values 10 times shorter than the phase coherence time t_2 measured at the same temperature. The experiments are interpreted by the N-spin model showing that t_R is directly associated with the decoherence via electronic/nuclear spin cross-relaxation in the rotating reference frame. It is shown that this decoherence is accompanied with energy dissipation in the range of the Rabi frequencies w_N - sigma_e < Omega_R < w_N, where sigma_e is the mean super-hyperfine field (in frequency units) induced by protons at SMMs. Weaker damping without dissipation takes place outside this dissipation window. Simple local field estimations suggest that this rapid cross-relaxation in resonant microwave field observed for the first time in SMMV_15 should take place in other SMMs like Fe_8 and Mn_12 containing protons, too

Normal Mode Determination of Perovskite Crystal Structures with Octahedral Rotations: Theory and Applications

Nuclear site analysis methods are used to enumerate the normal modes of $ABX_{3}$ perovskite polymorphs with octahedral rotations. We provide the modes of the fourteen subgroups of the cubic aristotype describing the Glazer octahedral tilt patterns, which are obtained from rotations of the $BX_{6}$ octahedra with different sense and amplitude about high symmetry axes. We tabulate all normal modes of each tilt system and specify the contribution of each atomic species to the mode displacement pattern, elucidating the physical meaning of the symmetry unique modes. We have systematically generated 705 schematic atomic displacement patterns for the normal modes of all 15 (14 rotated + 1 unrotated) Glazer tilt systems. We show through some illustrative examples how to use these tables to identify the octahedral rotations, symmetric breathing, and first-order Jahn-Teller anti-symmetric breathing distortions of the $BX_{6}$ octahedra, and the associated Raman selection rules. We anticipate that these tables and schematics will be useful in understanding the lattice dynamics of bulk perovskites and would serve as reference point in elucidating the atomic origin of a wide range of physical properties in synthetic perovskite thin films and superlattices.Comment: 17 pages, 3 figures, 17 tables. Supporting information accessed through link specified within manuscrip

Spin electric effects in molecular antiferromagnets

Molecular nanomagnets show clear signatures of coherent behavior and have a wide variety of effective low-energy spin Hamiltonians suitable for encoding qubits and implementing spin-based quantum information processing. At the nanoscale, the preferred mechanism for control of quantum systems is through application of electric fields, which are strong, can be locally applied, and rapidly switched. In this work, we provide the theoretical tools for the search for single molecule magnets suitable for electric control. By group-theoretical symmetry analysis we find that the spin-electric coupling in triangular molecules is governed by the modification of the exchange interaction, and is possible even in the absence of spin-orbit coupling. In pentagonal molecules the spin-electric coupling can exist only in the presence of spin-orbit interaction. This kind of coupling is allowed for both $s=1/2$ and $s=3/2$ spins at the magnetic centers. Within the Hubbard model, we find a relation between the spin-electric coupling and the properties of the chemical bonds in a molecule, suggesting that the best candidates for strong spin-electric coupling are molecules with nearly degenerate bond orbitals. We also investigate the possible experimental signatures of spin-electric coupling in nuclear magnetic resonance and electron spin resonance spectroscopy, as well as in the thermodynamic measurements of magnetization, electric polarization, and specific heat of the molecules.Comment: 31 pages, 24 figure

Magnetic exchange interaction in a pair of orbitally degenerate ions: Magnetic anisotropy of [Ti2Cl9]−3

The theory of the kinetic exchange in a pair of orbitally degenerate ions developed by the authors [J. Phys. Chem. A 102, 200 (1998)] is applied to the case of face-shared bioctahedral dimer (overall D3h-symmetry). The effective kinetic exchange Hamiltonian is found for a 2T2–2T2 system taking into account all relevant transfer pathways and charge-transfer crystal field states. The influence of different transfer integrals involved in the kinetic exchange on the energy pattern and magnetic properties of the system is examined. The role of other related interactions (trigonal crystal field, spin–orbit coupling) is also discussed in detail. Using the pseudoangular momentum representation and the technique of the irreducible tensor operators of R3-group we give a general outlook on the nontrivial symmetry properties of the effective Hamiltonian for the D3h-pair, and on the magnetic anisotropy arising from the orbital interactions specific for the case of orbital degeneracy. The magnetic properties of the binuclear unit [Ti2Cl9]−3 in Cs3Ti2Cl9 are discussed with a special emphasis on the magnetic anisotropy experimentally observed in this system. The existing exchange models for [Ti2Cl9]−3 and the concept of the effective Hamiltonian are discussed in the context of the present [email protected] ; [email protected] ; [email protected] ; [email protected]

Decoherence window and electron-nuclear cross relaxation in the molecular magnet V 15

Rabi oscillations in the V 15 single molecule magnet embedded in the surfactant (CH 3) 2[CH 3(CH 2) 16CH 2] 2N + have been studied at different microwave powers. An intense damping peak is observed when the Rabi frequency Ω R falls in the vicinity of the Larmor frequency of protons ω N. The experiments are interpreted by a model showing that the damping (or Rabi) time τ R is directly associated with decoherence caused by electron-nuclear cross relaxation in the rotating reference frame. This decoherence induces energy dissipation in the range ω N-σ e<Ω R<ω N, where σ e is the mean superhyperfine field induced by protons at V 15. Weaker decoherence without dissipation takes place outside this window. Specific estimations suggest that this rapid cross relaxation in a resonant microwave field, observed for the first time in V 15, should also take place, e.g., in Fe 8 and Mn 12. © 2012 American Physical Society

High‐nuclearity mixed‐valence magnetic clusters : A general solution of the double exchange problem

We report here a general solution of the double‐exchange problem in the high‐nuclearity mixed valence systems containing arbitrary number P of the electrons delocalized over the network of N (P<N) localized spins. The developed approach is based on the successive (chainlike) spin‐coupling scheme and takes full advantage from the quantum angular momentum theory. In the framework of this approach the closed‐form analytical expressions are deduced for the matrix elements of the double exchange interaction, two‐electron transfer, and three‐center interaction that can be referred to as the potential exchange transfer. For the arbitrary nuclearity mixed‐valence systems the matrix elements of all named interactions are expressed in terms of all relevant spin quantum numbers and 6j symbols and do not contain higher order recoupling coefficients. We describe also the combined approach taking into account both angular momentum consideration and advantages of point symmetry adapted basis [email protected] , [email protected] ; [email protected] ; [email protected] ; [email protected]

Electron-spin-resonance in the doped spin-Peierls compound Cu(1-x)Ni(x)GeO3

ESR-study of the Ni-doped spin-Peierls compound CuGeO3 has been performed in the frequency range 9-75 GHz. At low temperatures the g-factor is smaller than the value expected for Cu- and Ni-ions. This anomaly is explained by the formation of magnetic clusters around the Ni-ions within a nonmagnetic spin-Peierls matrix. The transition into the AFM-state detected earlier by neutron scattering for doped samples was studied by means of ESR. For x=0.032 a gap in the magnetic resonance spectrum is found below the Neel temperature and the spectrum is well described by the theory of antiferromagnetic resonance based on the molecular field approximation. For x=0.017 the spectrum below the Neel point remained gapless. The gapless spectrum of the antiferromagnetic state in weekly doped samples is attributed to the small value of the Neel order parameter and to the magnetically disordered spin-Peierls background.Comment: 16 pages, LATEX, 12 figures, submitted to Journal of Physics : Condensed Matte

Magnetic Resonance of the Intrinsic Defects of the Spin-Peierls Magnet CuGeO3

ESR of the pure monocrystals of CuGeO3 is studied in the frequency range 9-75 GHz and in the temperature interval 1.2-25 K. The splitting of the ESR line into several spectral components is observed below 5 K, in the temperature range where the magnetic susceptibility is suppressed by the spin-Peierls dimerization. The analysis of the magnetic resonance signals allows one to separate the signals of the S=1/2- and S=1 defects of the spin-Peierls phase. The value of g-factor of these signals is close to that of the Cu-ion. The additional line of the magnetic resonance is characterized by an anomalous value of the g-factor and by the threshold-like increase of the microwave susceptibility when the microwave power is increasing. The ESR signals are supposingly attributed to two types of the planar magnetic defects, arising at the boundaries of the domains of the spin-Peierls state with the different values of the phase of the dimerization.Comment: LATEX-text, 12 PS-figures, typos corrected, LATEX-style change

Calculating the energy spectra of magnetic molecules: application of real- and spin-space symmetries

The determination of the energy spectra of small spin systems as for instance given by magnetic molecules is a demanding numerical problem. In this work we review numerical approaches to diagonalize the Heisenberg Hamiltonian that employ symmetries; in particular we focus on the spin-rotational symmetry SU(2) in combination with point-group symmetries. With these methods one is able to block-diagonalize the Hamiltonian and thus to treat spin systems of unprecedented size. In addition it provides a spectroscopic labeling by irreducible representations that is helpful when interpreting transitions induced by Electron Paramagnetic Resonance (EPR), Nuclear Magnetic Resonance (NMR) or Inelastic Neutron Scattering (INS). It is our aim to provide the reader with detailed knowledge on how to set up such a diagonalization scheme.Comment: 29 pages, many figure