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

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.

Enhancing the blocking temperature in single-molecule magnets by incorporating 3d-5d exchange interactions.

We report the first single-molecule magnet (SMM) to incorporate the [Os(CN)(6)](3-) moiety. The compound (1) has a trimeric, cyanide-bridged Mn(III)-Os(III)-Mn(III) skeleton in which Mn(III) designates a [Mn(5-Brsalen)(MeOH)](+) unit (5-Brsalen=N,N'-ethylenebis(5-bromosalicylideneiminato)). X-ray crystallographic experiments reveal that 1 is isostructural with the Mn(III)-Fe(III)-Mn(III) analogue (2). Both compounds exhibit a frequency-dependent out-of-phase χ''(T) alternating current (ac) susceptibility signal that is suggestive of SMM behaviour. From the Arrhenius expression, the effective barrier for 1 is found to be Δ(eff)/k(B)=19 K (τ(0)=5.0×10(-7) s; k(B)=Boltzmann constant), whereas only the onset (1.5 kHz, 1.8 K) of χ''(T) is observed for 2, thus indicating a higher blocking temperature for 1. The strong spin-orbit coupling present in Os(III) isolates the E'(1g(1/2))(O(h)*) Kramers doublet that exhibits orbital contributions to the single-ion anisotropy. Magnetic susceptibility and inelastic neutron-scattering measurements reveal that substitution of [Fe(CN)(6)](3-) by the [Os(CN)(6)](3-) anion results in larger ferromagnetic, anisotropic exchange interactions going from quasi-Ising exchange interactions in 2 to pure Ising exchange for 1 with J(parallel)(MnOs)=-30.6 cm(-1). The combination of diffuse magnetic orbitals and the Ising-type exchange interaction effectively contributes to a higher blocking temperature. This result is in accordance with theoretical predictions and paves the way for the design of a new generation of SMMs with enhanced SMM properties.

Ground-state electronic structure of vanadium(III) trisoxalate in hydrated compounds.

The ground-state electronic structures of K3V(ox)3.3H2O, Na3V(ox)3.5H2O, and NaMgAl1-xVx(ox)3.9H2O (0 < x 1Gamma(t2g2) spin-forbidden electronic origins and inelastic neutron scattering measurements of the pseudo-octahedral [V(ox)3]3- complex anion below 30 K exhibit both axial and rhombic components to the zero-field-splittings (ZFSs). Analysis of the ground-state ZFS using the conventional S = 1 spin Hamiltonian reveals that the axial ZFS component changes sign from positive values for K3V(ox)3.3H2O (D approximately +5.3 cm-1) and Na3V(ox)3.5H2O (D approximately +7.2 cm-1) to negative values for NaMgAl1-xVx(ox)3.9H2O (D approximately -9.8 cm-1 for x = 0.013, and D approximately -12.7 cm-1 for x = 1) with an additional rhombic component, |E|, that varies between approximately 0.8 and approximately 2 cm-1. On the basis of existing crystallographic data, this phenomenon can be identified as due to variations in the axial and rhombic ligand fields resulting from outer-sphere H-bonding between crystalline water molecules and the oxalate ligands. Spectroscopic evidence of a crystallographic phase change is also observed for K3V(ox)3.3Y2O (Y = H or D) with three distinct lattice sites below 30 K, each with a unique ground-state electronic structure.

Single-ion anisotropy and exchange interactions in the cyano-bridged trimers MnIII2MIII(CN)6 (MIII = Co, Cr, Fe) species incorporating [Mn(5-Brsalen)]+ units: an inelastic neutron scattering and magnetic susceptibility study.

The electronic structures of the compounds K[(5-Brsalen)(2)(H(2)O)(2)-Mn(2)M(III)(CN)(6)].2H(2)O (M(III) = Co(III), Cr(III), Fe(III)) have been determined by inelastic neutron scattering (INS) and magnetic susceptibility studies, revealing the manganese(III) single-ion anisotropy and exchange interactions that define the low-lying states of the Mn-M(III)-Mn trimeric units. Despite the presence of an antiferromagnetic intertrimer interaction, the experimental evidence supports the classification of both the Cr(III) and Fe(III) compounds as single-molecule magnets. The value of 17(2) cm(-1) established from AC susceptibility measurements for a spin-reversal barrier of K[(5-Brsalen)(2)(H(2)O)(2)-Mn(2)Cr(CN)(6)].2H(2)O may be readily rationalized in terms of the energy level diagram determined directly by INS. AC susceptibility measurements on samples of K[(5-Brsalen)(2)(H(2)O)(2)-Mn(2)Fe(CN)(6)].2H(2)O are contrary to those previously reported, exhibiting but the onset of peaks below temperatures of 1.8 K at oscillating frequencies in the range of 100-800 Hz. INS measurements reveal an anisotropic ferromagnetic manganese(III)-iron(III) exchange interaction, in accordance with theoretical expectations based on the unquenched orbital angular momentum of the [Fe(CN)(6)](3-) anion, giving rise to an M(s) approximately +/-9/2 ground state, isolated by approximately 11.5 cm(-1) from the higher-lying levels. The reported INS and magnetic data should now serve as a benchmark against which theoretical models that aim to inter-relate the electronic and molecular structure of molecular magnets should be tested.

The dynamic Jahn-Teller effect in Cu(II) doped MgO.

The electron paramagnetic resonance spectra of Cu(II) doped MgO single crystals have been re-examined in detail within the framework of a dynamic Jahn-Teller effect. The experimental 1.8 K X-band spectra can be modeled in terms of a cubic spin Hamiltonian operating within the set of four Kramers doublets corresponding to the lowest vibronic energy levels of an Emultiply sign in circlee Jahn-Teller problem. This "four state" model must also include vibronic (Ham) reduction factors and a random distribution of the crystal strain. It was found to be important to treat the Zeeman, hyperfine, quadrupole, tunneling, and strain terms without recourse to perturbation theory or other approximations and this has been carried out using the eigenfield method. We find that the first excited singlet is of A(2) symmetry, indicating that the CuO(6) center has the expected Emultiply sign in circlee Jahn-Teller potential energy surface with three equivalent minima at tetragonally elongated octahedral geometries. Small random crystal strains have a dominant influence on the spectra and we find that the major features can be reproduced by averaging over the strain in the angular direction phi(s) with a small magnitude centered about zero. Details of the strain broadening require a distribution of strains centered at zero with a larger spread; however, the use of a single intrinsic linewidth could not account for all linewidth features. Our analysis also differs from that of previous workers in that different hyperfine values (A(1)=-20.0 x 10(-4) and A(2)=-86.0 x 10(-4) cm(-1)) are required as well as a nuclear quadrupole term (P(2)=+8.75 x 10(-4) cm(-1)) to account for the observed structure and the angular dependence. The transitions within the lowest excited singlet are observed directly, giving an estimate of the tunneling splitting as approximately 4 cm(-1). These parameter values are related to the intrinsic Jahn-Teller coupling parameters of the potential energy surface. We conclude that the Cu(II)/MgO system can be described as an almost pure dynamic Jahn-Teller case, with most spectral features accounted for by using a single isolated Gamma(8)((2)E) vibronic state.

DAVE: A Comprehensive Software Suite for the Reduction, Visualization, and Analysis of Low Energy Neutron Spectroscopic Data.

National user facilities such as the NIST Center for Neutron Research (NCNR) require a significant base of software to treat the data produced by their specialized measurement instruments. There is no universally accepted and used data treatment package for the reduction, visualization, and analysis of inelastic neutron scattering data. However, we believe that the software development approach adopted at the NCNR has some key characteristics that have resulted in a successful software package called DAVE (the Data Analysis and Visualization Environment). It is developed using a high level scientific programming language, and it has been widely adopted in the United States and abroad. In this paper we describe the development approach, elements of the DAVE software suite, its usage and impact, and future directions and opportunities for development.

Single-Crystal Raman Spectroscopy of the Rubidium Alums RbM(III)(SO(4))(2).12H(2)O (M(III) = Al, Ga, In, Ti, V, Cr, Fe) between 275 and 1200 cm(-)(1): Correlation between the Electronic Structure of the Tervalent Cation and Structural Abnormalities.

Low-temperature single-crystal Raman spectra for RbM(III)(SO(4))(2).12H(2)O (M(III) = Al, Ga, In, Ti, V, Cr, Fe) and RbM(III)(SO(4))(2).12D(2)O (M(III) = Al, V) have been collected and assigned in the range 275-1200 cm(-)(1). These results permit classification of the Ti and V rubidium sulfate alums to the beta modification, whereas the remaining tervalent cations give the expected alpha modification. The dimorphism of the rubidium sulfate alums is explained in terms of the electronic structure of the tervalent cation, where the observation of the beta modification is associated with unequal occupancy of the t(2g) (O(h)()) orbitals. For the rubidium vanadium alums the (3)E(g) <-- (3)A(g) electronic Raman (eR) transition permits quantification of the trigonal field splitting of the t(2g) (O(h)()) orbitals (ca. 1940 cm(-)(1)). The profile of the eR band is sensitive both to changes in temperature and to deuteration. Analysis of the eR band profile suggests a reduced spin-orbit splitting of the (3)E(g) manifold, this being ascribed to excited state Jahn-Teller (J-T) effects. The similarity of the Raman spectra of the cesium and rubidium titanium sulfate alums suggest that they exhibit closely related structural chemistry, with both subject to phase transitions below 80 K. The observation that modes of E(g) symmetry are coupled to the structural change is consistent with the interpretation that the trigonal field leaves an orbital doublet ground term for titanium(III), leading to a cooperative J-T effect.

Spectroscopic effects resulting from interacting singlet and triplet excited states: vibronic structure involving the O-H stretching mode in d-d absorption bands of Ni(H2O)6(2+).

The ligand-field absorption spectrum of the Ni(H2O)6(2+) cation has been thoroughly measured and analyzed over the past sixty years, often on crystals with low symmetry at the metal site, and its absorption band maxima have been used as a benchmark for increasingly sophisticated electronic structure calculations over the last decades. We present variable-temperature absorption spectra measured on crystals with cubic Th symmetry at the site of the nickel(ii) cation. This high site symmetry is confirmed for CsNi(H2O)6PO4 by X-ray diffraction and allows for a direct comparison with ligand-field calculations in Th symmetry, at the basis of an analysis of the vibronic structure in the energy range of the lowest-energy spin-forbidden transition, the "red" or middle band of the spectrum. This spectroscopic region displays effects of strong interactions between singlet and triplet excited states, influencing intensities and vibronic structure. A particular feature that has not been analyzed in detail is a clearly discernible vibronic progression involving the O-H stretching mode on the high-energy side of the absorption band. A quantitative model is presented and applied in order to rationalize this unusual effect, originating from coupling between normal coordinates, to the best of our knowledge the first analysis of this distinct spectroscopic feature arising from interacting excited states.

Varying spin state composition by the choice of capping ligand in a family of molecular chains: detailed analysis of magnetic properties of chromium(III) horseshoes.

We report a detailed physical analysis on a family of isolated, antiferro-magnetically (AF) coupled, chromium(III) finite chains, of general formula (Cr(RCO(2))(2)F)(n) where the chain length n = 6 or 7. Additionally, the chains are capped with a selection of possible terminating ligands, including hfac (= l,l,l,5,5,5-hexafluoropentane-2,4-dionate(l-)), acac (= pentane-2,4-dionate(l-)) or (F)(3). Measurements by inelastic neutron scattering (INS), magnetometery and electron paramagnetic resonance (EPR) spectroscopy have been used to study how the electronic properties are affected by n and capping ligand type. These comparisons allowed the subtle electronic effects the choice of capping ligand makes for odd member spin 3/2 ground state and even membered spin 0 ground state chains to be investigated. For this investigation full characterisation of physical properties have been performed with spin Hamiltonian parameterisation, including the determination of Heisenberg exchange coupling constants and single ion axial and rhombic anisotropy. We reveal how the quantum spin energy levels of odd or even membered chains can be modified by the type of capping ligand terminating the chain. Choice of capping ligands enables Cr-Cr exchange coupling to be adjusted by 0, 4 or 24%, relative to Cr-Cr exchange coupling within the body of the chain, by the substitution of hfac, acac or (F)(3) capping ligands to the ends of the chain, respectively. The manipulation of quantum spin levels via ligands which play no role in super-exchange, is of general interest to the practise of spin Hamilton modelling, where such second order effects are generally not considered of relevance to magnetic properties.

Origin of compressed Jahn-Teller octahedra in sterically strained manganese(III) complexes.

A method is presented that enables the bond length changes resulting from the Jahn-Teller interaction to be predicted from a knowledge of the angular geometry of the complex and the identity of the ligators. The calculation of the energy minimum within the subspace of the Jahn-Teller active e skeletal mode proceeds by diagonalization of the potential energy component of the cubic Ee Jahn-Teller problem, incorporating low-symmetry distortions by way of angular overlap model calculations. The theory is applied to a series of manganese(III) complexes formed with tetradentate tripodal ligands that largely dictate the angular coordinates. A good account of the contrasting molecular structures is obtained by allowing the sigma-bonding strength to vary according to expectations based upon the spectrochemical series.

Theory of High-Spin d(4) Complexes: An Angular-Overlap Model Parametrization of the Ligand Field in Vibronic-Coupling Calculations.

A new theoretical approach for the calculation of the electronic and molecular structures of octahedrally-coordinated high-spin d(4) complexes is described. A prescription for the construction of an effective (3)T1 + (5)E (O) Hamiltonian from the ligand-field matrices of a complex with general trigonal symmetry is given, where the ligand field is parametrized in terms of the angular-overlap model (AOM). The Jahn-Teller matrices for the (3)T1 + ((5)E⊗e) vibronic Hamiltonian are constructed and the lowest eigenvalues are calculated by a numerical method. The model obviates the need to assume a temperature dependence of bonding parameters, inherent to the conventional ligand-field-theory approach and is applicable over the whole range of vibronic-coupling strengths, as demonstrated by example calculations on the [Mn(OD2)6](3+) cation and MgO:Cr(2+).

Spectroscopic and theoretical study of a mononuclear manganese(III) complex exhibiting a tetragonally compressed geometry.

Inelastic neutron scattering and high-field electron paramagnetic resonance data are presented for [Mn(bpia)(OAc)(OCH(3))](PF(6)), where bpia is bis(picolyl)(N-methylimidazole-2-yl)amine. Modeling of the data to the conventional fourth-order spin-Hamiltonian yielded the following parameters: D = 3.526(3) cm(-1), E = 0.588(6) cm(-1), B(0)(4) = -0.00084(7) cm(-1), B(2)( 4)= -0.002(2) cm(-1), (4)(4) = -0.0082(5) cm(-1), g(x) = 1.98(1), g(y) = 1.952(6), and g(z) = 1.978(5). The complex is of particular interest given the biochemical activity and the unusual stereochemistry distinguished by a rare example of a tetragonally compressed octahedron and a pronounced angular distortion imposed by the tetradentate tripodal bpia ligand. Ligand field, density functional theory, and complete active space self-consistent field ab initio calculations are presented that aim to relate the spectroscopic data to the molecular geometry.

Pressure-induced switch of the direction of the unique Jahn-Teller axis of the chromium(II) hexaqua cation in the deuterated ammonium chromium Tutton salt.

Inelastic neutron scattering (INS) spectra are presented for chromium(II) Tutton salts, as a function of the temperature and pressure. Transitions are observed between the levels of the 5Ag (Ci) ground term and the data modeled with a conventional S = 2 spin Hamiltonian. At 10 K and ambient pressure, the zero-field-splitting parameters of the ammonium salt, (ND4)2Cr(D2O)6(SO4)2, are determined as D = -2.431(4) cm(-1) and E = 0.091(4) cm(-1), evolving to D = -2.517(4) cm(-1) and E = 0.127(5) cm(-1) upon application of 7.5(1.0) kbar of quasi-hydrostatic pressure. By contrast, the change in the INS spectrum of the rubidium salt in this pressure range is comparitively minor. The results are interpreted using a 5Ee vibronic-coupling Hamiltonian, in which low-symmetry strain, perturbing the adiabatic potential-energy surface, is pressure-dependent. It is argued that, for the ammonium salt, the change with pressure of the anisotropic strain impinging upon the [Cr(D2O)6]2+ cation is sufficient to cause a switch of the long and intermediate Cr-OD2 bonds, with respect to the crystallographic axes.

The electronic ground state of [V(urea)6]3+ probed by NIR luminescence, electronic Raman, and high-field EPR spectroscopies.

The electronic structure of a trigonally distorted vanadium(III) complex, [V(urea)6](ClO4)3, and its deuterated analogue, [V(urea-d4)6](ClO4)3 has been investigated with Raman, luminescence, and high-frequency high-field electron paramagnetic resonance spectroscopies and with magnetic measurements. A broad electronic Raman transition is observed at around 1400 cm(-1) and attributed to a transition to the (3)E (D3) component of the (3)T1g (O(h)) ground state. The same splitting is seen in the near-infrared luminescence spectrum in the form of a similarly broad peak at 8450 cm(-1), 1400 cm(-1) lower in energy than the (1)E --> (3)A2 spin-flip transition. Powder high-frequency and high-field electron paramagnetic resonance spectra, magnetic susceptibilities, and magnetization studies give a precise measurement of the zero-field splitting and of the g values in this complex (D = 6.00(2) cm(-1), E = 0.573(6) cm(-1), g(x) = 1.848(2), g(y) = 1.832(4), and g(z) = 1.946(7)). A set of angular overlap model parameters is proposed that reproduces all spectroscopic observations, and an analysis of the influence of the bonding of urea on the trigonal distortion of the complex is given.

Spectroscopic, magnetochemical, and crystallographic study of cesium iron phosphate hexahydrate: characterization of the electronic structure of the iron(II) hexa-aqua cation in a quasicubic environment.

Spectroscopic, magnetochemical, and crystallographic data are presented for CsFe(H2O)6PO4, a member of a little-known isomorphous series of salts that facilitates the study of hexa-aqua ions in a quasicubic environment. Above 120 K, the deviations from cubic symmetry are minimal, as shown by the first example of an iron(II) Mössbauer spectrum that exhibits no measurable quadrupole splitting. Two crystallographically distinct [Fe(OH2)6]2+ complexes are identified from inelastic neutron-scattering (INS) experiments conducted between 2 and 15 K. The data are modeled with the ligand-field Hamiltonian, H = lambdaLs + betaB(kL + 2s) + Delta(tet){Lz2 - (1/3)L(L + 1)} + Delta(rhom){Lx2 - Ly2}, operating in the ground-term (5)T(2g) (Oh) basis. An excellent reproduction of INS, Mössbauer, HF-EPR, and magnetochemical data are obtained in the 2 and 15 K temperature regimes with the following parameters: lambda = -80 cm(-1); k = 0.8; site A Delta(tet) = 183 cm(-1), Delta(rhom)= 19 cm(-1); site B Delta(tet) = 181 cm(-1), Delta(rhom)= 12 cm(-1). The corresponding zero-field-splitting (ZFS) parameters of the conventional S = 2 spin Hamiltonian are as follows: site A D = 12.02 cm(-)(1), E = 2.123 cm(-1); site B D = 12.15 cm(-1), E = 1.37 cm(-1). A theoretical analysis of the variation of the energies of the low-lying states with respect to displacements along selected normal coordinates of the [Fe(OH2)6]2+, shows the zero-field splitting to be extremely sensitive to small structural perturbations of the complex. The expressions derived are discussed in the context of spin-Hamiltonian parameters reported for the [Fe(OH2)6]2+ cation in different crystalline environments.

Electronic Raman spectroscopy of the vanadium(III) hexaaqua cation in guanidinium vanadium sulphate: Quintessential manifestation of the dynamical Jahn-Teller effect.

Single-crystal Raman spectra are presented for the salt [C(NH2)3][V(OH2)6](SO4)2, displaying electronic transitions between the trigonal components of the vanadium(III) 3T1g(Oh) ground term. The 3A-->3E(C3) electronic Raman band is centered at approximately 2720 cm-1, and exhibits extensive structure, revealing the energies of the spinor components of the 3E(C3) term for the two crystallographically distinct [V(OH2)6]3+ cations. The data are interpreted in conjunction with parameters previously reported from an electron paramagnetic resonance study of the salt. A satisfactory reproduction of the electronic Raman profile and ground-state spin-Hamiltonian parameters is achieved by employing a (3A plus sign in circle3E)multiply sign in circle e vibronic coupling model, in which the spin-orbit splitting of the 3E(C3) is quenched significantly by the Ham effect, and the intensity of harmonics of the Jahn-Teller active vibration enhanced by their proximity to the electronic Raman bands. The model gives an excellent account of the intensities of the electronic Raman bands, which are shown to depend profoundly on both temperature and the selected component of the polarizability tensor. The electronic Raman profile changes notably upon deuteriation, a result that exposes deficiencies in the single-mode coupling model.

Structure and bonding of the vanadium(III) hexa-aqua cation. 2. Manifestation of dynamical Jahn-Teller coupling in axially distorted vanadium(III) complexes.

Ground-state spin-Hamiltonian parameters, magnetic data, and electronic Raman spectra of hexacoordinate vanadium(III) complexes are calculated with consideration to the ((3)A (3)E) e vibronic interaction and compared to experimental data. It is shown that the zero-field-splitting of the (3)A(g) (S(6)) ground term may be reduced significantly by the dynamical Jahn-Teller effect, particularly when the pi-anisotropy of the metal-ligand bonding interaction is significant, and the energy of the Jahn-Teller active vibration is comparable to the diagonal axial field. The dynamical Jahn-Teller effect may also give rise to a significant enhancement in the Raman intensity of overtones and higher harmonics of Jahn-Teller active vibrations, when the energies of these transitions fall in the proximity of intra-(3)T(1g) (O(h)) electronic Raman transitions. A simple method of conducting vibronic coupling calculations is described, employing ligand field matrices generated by angular overlap model calculations, which may in principle be applied to any transition metal complex.

Aqua Ions. 1. The structures of the [Ru(OH(2))(6)](3+) and [V(OH(2))(6)](3+) cations in aqueous solution: an EPR and UV-Vis study.

Spectroscopic data are presented for the [V(OH(2))(6)](3+) and [Ru(OH(2))(6)](3+) cations, from which inferences are drawn regarding their structures in aqueous solution. EPR and absorption spectra of solutions and glasses are supplemented by spectra of the aqua ions in various crystalline environments, and the electronic and molecular structures inter-related through elementary angular overlap model calculations. It is concluded that in aqueous solution the [Ru(OH(2))(6)](3+) cation is localized in the all-horizontal D(3)(d)geometry, whereas the structure of the [V(OH(2))(6)](3+) cation is close to T(h) symmetry. These results are consistent with the most energetically favored geometries predicted by ab initio calculations.