High-Spin and Emissive Molecular Materials: Synthesis and Characterization of New Polynuclear Ni(II) Complexes from the Use of Aromatic Schiff Bases as Bridging Ligands

The employment of the bridging/chelating Schiff bases, N-salicylidene-4-methyl-o-aminophenol (samphH2) and N-naphthalidene-2-amino-5-chlorobenzoic acid (nacbH2), in nickel cluster chemistry has afforded eight polynuclear Ni(II) complexes with new structural motifs, interesting magnetic and optical properties, and unexpected organic ligand transformations. In the present thesis, Chapter 1 deals with all the fundamental aspects of polynuclear metal complexes, molecular magnetism and optics, while research results are reported in Chapters 2 and 3. In the first project (Chapter 2), I investigated the coordination chemistry of the organic chelating/bridging ligand, N-salicylidene-4-methyl-o-aminophenol (samphH2). The general NiII/tBuCO2-/samphH2 reaction system afforded two new tetranuclear NiII clusters, namely [Ni4(samph)4(EtOH)4] (1) and [Ni4(samph)4(DMF)2] (2), with different structural motifs. Complex 1 possessed a cubane core while in complex 2 the four NiII ions were located at the four vertices of a defective dicubane. The nature of the organic solvent was found to be of pivotal importance, leading to compounds with the same nuclearity, but different structural topologies and magnetic properties. The second project, the results of which are summarized in Chapter 3, included the systematic study of a new optically-active Schiff base ligand, N-naphthalidene-2-amino-5-chlorobenzoic acid (nacbH2), in NiII cluster chemistry. Various reactions between NiX2 (X- = inorganic anions) and nacbH2 were performed under basic conditions to yield six new polynuclear NiII complexes, namely (NHEt3)[Ni12(nacb)12(H2O)4](ClO4) (3), (NHEt3)2[Ni5(nacb)4(L)(LH)2(MeOH)] (4), [Ni5(OH)2(nacb)4(DMF)4] (5), [Ni5(OMe)Cl(nacb)4(MeOH)3(MeCN)] (6), (NHEt3)2[Ni6(OH)2(nacb)6(H2O)4] (7), and [Ni6(nacb)6(H2O)3(MeOH)6] (8). The nature of the solvent, the inorganic anion, X-, and the organic base were all found to be of critical importance, leading to products with different structural topologies and nuclearities (i.e., {Ni5}, {Ni6} and {Ni12}). Magnetic studies on all synthesized complexes revealed an overall ferromagnetic behavior for complexes 4 and 8, with the remaining complexes being dominated by antiferromagnetic exchange interactions. In order to assess the optical efficiency of the organic ligand when bound to the metal centers, photoluminescence studies were performed on all synthesized compounds. Complexes 4 and 5 show strong emission in the visible region of the electromagnetic spectrum. Finally, the ligand nacbH2 allowed for some unexpected organic transformations to occur; for instance, the pentanuclear compound 5 comprises both nacb2- groups and a new organic chelate, namely the anion of 5-chloro-2-[(3-hydroxy-4-oxo-1,4-dihydronaphthalen-1-yl)amino]benzoic acid. In the last section of this thesis, an attempt to compare the NiII cluster chemistry of the N-naphthalidene-2-amino-5-chlorobenzoic acid ligand with that of the structurally similar but less bulky, N-salicylidene-2-amino-5-chlorobenzoic acid (sacbH2), was made.

Systèmes superintégrables avec spin et intégrales du mouvement d’ordre deux

Ce mémoire est une partie d’un programme de recherche qui étudie la superintégrabilité des systèmes avec spin. Plus particulièrement, nous nous intéressons à un hamiltonien avec interaction spin-orbite en trois dimensions admettant une intégrale du mouvement qui est un polynôme matriciel d’ordre deux dans l’impulsion. Puisque nous considérons un hamiltonien invariant sous rotation et sous parité, nous classifions les intégrales du mouvement selon des multiplets irréductibles de O(3). Nous calculons le commutateur entre l’hamiltonien et un opérateur général d’ordre deux dans l’impulsion scalaire, pseudoscalaire, vecteur et pseudovecteur. Nous donnons la classification complète des systèmes admettant des intégrales du mouvement scalaire et vectorielle. Nous trouvons une condition nécessaire à remplir pour le potentiel sous forme d’une équation différentielle pour les cas pseudo-scalaire et pseudo-vectoriel. Nous utilisons la réduction par symétrie pour obtenir des solutions particulières de ces équations.

Asymmetric Little spin-Glass model

We study the static properties of the Little model with asymmetric couplings. We show that the thermodynamics of this model coincides with that of the Sherrington-Kirkpatrick model, and we compute the main finite-size corrections to the difference of the free energy between these two models and to some clarifying order parameters. Our results agree with numerical simulations. Numerical results are presented for the symmetric Little model, which show that the same conclusions are also valid in this case.

Theoretical study of magnetism, structure and chemical order in transition-metal alloy clusters

Research on transition-metal nanoalloy clusters composed of a few atoms is fascinating by their unusual properties due to the interplay among the structure, chemical order and magnetism. Such nanoalloy clusters, can be used to construct nanometer devices for technological applications by manipulating their remarkable magnetic, chemical and optical properties. Determining the nanoscopic features exhibited by the magnetic alloy clusters signifies the need for a systematic global and local exploration of their potential-energy surface in order to identify all the relevant energetically low-lying magnetic isomers. In this thesis the sampling of the potential-energy surface has been performed by employing the state-of-the-art spin-polarized density-functional theory in combination with graph theory and the basin-hopping global optimization techniques. This combination is vital for a quantitative analysis of the quantum mechanical energetics. The first approach, i.e., spin-polarized density-functional theory together with the graph theory method, is applied to study the Fe$_m$Rh$_n$ and Co$_m$Pd$_n$ clusters having $N = m+n \leq 8$ atoms. We carried out a thorough and systematic sampling of the potential-energy surface by taking into account all possible initial cluster topologies, all different distributions of the two kinds of atoms within the cluster, the entire concentration range between the pure limits, and different initial magnetic configurations such as ferro- and anti-ferromagnetic coupling. The remarkable magnetic properties shown by FeRh and CoPd nanoclusters are attributed to the extremely reduced coordination number together with the charge transfer from 3$d$ to 4$d$ elements. The second approach, i.e., spin-polarized density-functional theory together with the basin-hopping method is applied to study the small Fe$_6$, Fe$_3$Rh$_3$ and Rh$_6$ and the larger Fe$_{13}$, Fe$_6$Rh$_7$ and Rh$_{13}$ clusters as illustrative benchmark systems. This method is able to identify the true ground-state structures of Fe$_6$ and Fe$_3$Rh$_3$ which were not obtained by using the first approach. However, both approaches predict a similar cluster for the ground-state of Rh$_6$. Moreover, the computational time taken by this approach is found to be significantly lower than the first approach. The ground-state structure of Fe$_{13}$ cluster is found to be an icosahedral structure, whereas Rh$_{13}$ and Fe$_6$Rh$_7$ isomers relax into cage-like and layered-like structures, respectively. All the clusters display a remarkable variety of structural and magnetic behaviors. It is observed that the isomers having similar shape with small distortion with respect to each other can exhibit quite different magnetic moments. This has been interpreted as a probable artifact of spin-rotational symmetry breaking introduced by the spin-polarized GGA. The possibility of combining the spin-polarized density-functional theory with some other global optimization techniques such as minima-hopping method could be the next step in this direction. This combination is expected to be an ideal sampling approach having the advantage of avoiding efficiently the search over irrelevant regions of the potential energy surface.

First-principles electronic theory of non-collinear magnetic order in transition-metal nanowires

The structural, electronic and magnetic properties of one-dimensional 3d transition-metal (TM) monoatomic chains having linear, zigzag and ladder geometries are investigated in the frame-work of first-principles density-functional theory. The stability of long-range magnetic order along the nanowires is determined by computing the corresponding frozen-magnon dispersion relations as a function of the 'spin-wave' vector q. First, we show that the ground-state magnetic orders of V, Mn and Fe linear chains at the equilibrium interatomic distances are non-collinear (NC) spin-density waves (SDWs) with characteristic equilibrium wave vectors q that depend on the composition and interatomic distance. The electronic and magnetic properties of these novel spin-spiral structures are discussed from a local perspective by analyzing the spin-polarized electronic densities of states, the local magnetic moments and the spin-density distributions for representative values q. Second, we investigate the stability of NC spin arrangements in Fe zigzag chains and ladders. We find that the non-collinear SDWs are remarkably stable in the biatomic chains (square ladder), whereas ferromagnetic order (q =0) dominates in zigzag chains (triangular ladders). The different magnetic structures are interpreted in terms of the corresponding effective exchange interactions J(ij) between the local magnetic moments μ(i) and μ(j) at atoms i and j. The effective couplings are derived by fitting a classical Heisenberg model to the ab initio magnon dispersion relations. In addition they are analyzed in the framework of general magnetic phase diagrams having arbitrary first, second, and third nearest-neighbor (NN) interactions J(ij). The effect of external electric fields (EFs) on the stability of NC magnetic order has been quantified for representative monoatomic free-standing and deposited chains. We find that an external EF, which is applied perpendicular to the chains, favors non-collinear order in V chains, whereas it stabilizes the ferromagnetic (FM) order in Fe chains. Moreover, our calculations reveal a change in the magnetic order of V chains deposited on the Cu(110) surface in the presence of external EFs. In this case the NC spiral order, which was unstable in the absence of EF, becomes the most favorable one when perpendicular fields of the order of 0.1 V/Å are applied. As a final application of the theory we study the magnetic interactions within monoatomic TM chains deposited on graphene sheets. One observes that even weak chain substrate hybridizations can modify the magnetic order. Mn and Fe chains show incommensurable NC spin configurations. Remarkably, V chains show a transition from a spiral magnetic order in the freestanding geometry to FM order when they are deposited on a graphene sheet. Some TM-terminated zigzag graphene-nanoribbons, for example V and Fe terminated nanoribbons, also show NC spin configurations. Finally, the magnetic anisotropy energies (MAEs) of TM chains on graphene are investigated. It is shown that Co and Fe chains exhibit significant MAEs and orbital magnetic moments with in-plane easy magnetization axis. The remarkable changes in the magnetic properties of chains on graphene are correlated to charge transfers from the TMs to NN carbon atoms. Goals and limitations of this study and the resulting perspectives of future investigations are discussed.

A ferromagnetic methoxido-bridged Mn(III) dimer and a spin-canted metamagnetic μ1,3-azido-bridged chain

Two new Mn(III) complexes of formulas [MnL1(N-3)(OMe)](2) (1) and [MnL2(N-3)(2)](n) (2) have been synthesized by using two tridentate NNO-donor Schiff base ligands HL1{(2-[(3-methylaminoethylimino)-methyl]-phenol)} and HL2 {(2-[1-(2-dimethylaminoethylimino)methyl]-phenol)}, respectively. Substitution of the H atom on the secondary amine group of the N-methyldiamine fragment of the Schiff base by a methyl group leads to a drastic structural change from a methoxido-bridged dimer (1) to a single mu(1,3)-azido-bridged 1D helical polymer (2). Both complexes were characterized by single-crystal X-ray structural analyses and variable-temperature magnetic susceptibility measurements. The magnetic properties of compound I show the presence of weak ferromagnetic exchange interactions mediated by double methoiddo bridges (J = 0.95 cm(-1)). Compound 2 shows the existence of a weak antiferromangetic coupling along the chain (J = -8.5 cm(-1)) through the single mu(1,3)-N-3 bridge with a spin canting that leads to a long-range antiferromagnetic order at T-c approximate to 9.3 K and a canting leading to a weak ferromagnetic long-range order at T-c approximate to 8.5 K. It also exibits metamagnetic behavior at low temperatures with a critical field of ca.1.2 T due to the weak antiferromagnetic interchain interactions that appear in the canted ordered phase.

Spin-canted antiferromagnetic phase transitions in alternating phenoxo- and carboxylato-bridged Mn(III)-salen complexes

Three new MnIII complexes, {[Mn-2(salen)(2)(OCn)](ClO4)}(n) (1), {[Mn-2(salen)(2)(OPh)](ClO4)}(n) (2) and {[Mn-2(salen)(2)(OBz)](ClO4)}(2) (3) (where salen = N,N'-bis(salicylidene)-1,2-diaminoethane dianion, OCn = cinnamate, OPh = phenylacetate and OBz = benzoate), have been synthesized and characterized structurally and magnetically. The crystal structures reveal that all three structures contain syn-anti carboxylatebridged dimeric [Mn-2(salen)(2)(OOCR)](+) cations (OOCR = bridging carboxylate) that are joined together by weak Mn center dot center dot center dot O(phenoxo) interactions to form infinite alternating chain structures in 1 and 2, but the relatively long Mn center dot center dot center dot O(phenoxo) distance [3.621(2)angstrom] in 3 restricts this structure to tetranuclear units. Magnetic studies showed that 1 and 2 exhibited magnetic long-range order at T-N = 4.0 and 4.6 K (T-N = Neel transition temperature), respectively, to give spin-canted antiferromagnetic structures. Antiferromagnetic coupling was also observed in 3 but no peaks were recorded in the field-cooled magnetization (FCM) or zero-field-cooled magnetization (ZFCM) data, indicating that 3 remained paramagnetic down to 2 K. This dominant antiferromagnetic coupling is attributed to the carboxylate bridges. The ferromagnetic coupling expected due to the Mn-O(phenoxo)center dot center dot center dot Mn bridge plays an auxiliary role in the magnetic chain, but is an essential component of the bulk magnetic properties of the material.

Next-to-leading order QCD corrections to the polarized hadroproduction of heavy flavors

We present the complete next-to-leading order QCD corrections to the polarized hadroproduction of heavy flavors which soon will be studied experimentally in polarized pp collisions at the BNL Relativistic Heavy Ion Collider (RHIC) in order to constrain the polarized gluon density Δg. It is demonstrated that the dependence on unphysical renormalization and factorization scales is strongly reduced beyond the leading order. The sensitivity of the charm quark spin asymmetry to Δg is analyzed in some detail, including the limited detector acceptance for leptons from charm quark decays at the BNL RHIC.

Photoproduction of heavy quarks in next-to-leading order QCD with longitudinally polarized initial states

We present all relevant details of our calculation of the complete next-to-leading order O(αS2α) QCD corrections to heavy flavor photoproduction with longitudinally polarized point-like photons and hadrons. In particular we provide analytical results for the virtual plus soft gluon cross section. We carefully address the relevance of remaining theoretical uncertainties by varying, for instance, the factorization and renormalization scales independently. Such studies are of importance for a meaningful first direct determination of the polarized gluon density Δg from the total charm production spin asymmetry by the upcoming COMPASS experiment. It is shown that the scale uncertainty is considerably reduced in next-to-leading order, but the dependence on the charm quark mass is sizable at fixed target energies. Finally, we study several differential single-inclusive heavy quark distributions and, for the polarized HERA option, the total bottom spin asymmetry.

Next-to-leading order QCD corrections to the polarized photoproduction of heavy flavors

We present a calculation of the next-to-leading order ... QCD corrections to heavy flavor photoproduction with longitudinally polarized beams. We apply our results to study the longitudinal spin asymmetry for the total charm quark production cross section which will be utilized by the forthcoming COMPASS experiment at CERN to obtain first direct information on the polarized gluon density Δg. We also briefly discuss the main theoretical uncertainties inherent in this calculation. In particular we demonstrate that the factorization scale dependence is considerably reduced in next-to-leading order.

Spin equilibrium and outflows in young stellar objects

We present N-body simulations of accretion discs about young stellar objects (YSOs). The simulation includes the presence of a magnetic loop structure on the central star which interacts with the particles by means of a magnetic drag force. We find that an equilibrium spin rate is achieved when the corotation radius coincides with the edge of the loop. This spin rate is consistent with observed values for TTauri stars, being an order of magnitude less than the breakup value. The material ejected from the system by the rotating loop has properties consistent with the observed molecular outflows, given the presence of a suitable containing cavity.

Spin-polarized electronic-structure of MnBiAl

The self-consistent spin-polarized band-structure calculation of ferromagnetic compound MnBiAl in its low-temperature phase has been performed. In this paper the calculation results are given. Comparison with the results of MnBi is performed in order to find the effect on electronic structure by doping with Al.

Hydrodynamics with spin angular momentum from systematic coarse graining: a tutorial example

The derivation of time evolution equations for slow collective variables starting from a micro- scopic model system is demonstrated for the tutorial example of the classical, two-dimensional XY model. Projection operator techniques are used within a nonequilibrium thermodynamics framework together with molecular simulations in order to establish the building blocks of the hydrodynamics equations: Poisson brackets that determine the deterministic drift, the driving forces from the macroscopic free energy and the friction matrix. The approach is rather general and can be applied for deriving the equations of slow variables for a broad variety of systems.

Extending the use of canonical and microcanonical Monte Carlo algorithms to spin models

We describe the canonical and microcanonical Monte Carlo algorithms for different systems that can be described by spin models. Sites of the lattice, chosen at random, interchange their spin values, provided they are different. The canonical ensemble is generated by performing exchanges according to the Metropolis prescription whereas in the microcanonical ensemble, exchanges are performed as long as the total energy remains constant. A systematic finite size analysis of intensive quantities and a comparison with results obtained from distinct ensembles are performed and the quality of results reveal that the present approach may be an useful tool for the study of phase transitions, specially first-order transitions. (C) 2009 Elsevier B.V. All rights reserved.

Compressible Sherrington-Kirkpatrick spin-glass model

We introduce a Sherrington-Kirkpatrick spin-glass model with the addition of elastic degrees of freedom. The problem is formulated in terms of an effective four-spin Hamiltonian in the pressure ensemble, which can be treated by the replica method. In the replica-symmetric approximation, we analyze the pressure-temperature phase diagram, and obtain expressions for the critical boundaries between the disordered and the ordered (spin-glass and ferromagnetic) phases. The second-order para-ferromagnetic border ends at a tricritical point, beyond which the transition becomes discontinuous. We use these results to make contact with the temperature-concentration phase diagrams of mixtures of hydrogen-bonded crystals.