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.

Normative and cognitive influences on female entrepreneurial reluctance at the base of the pyramid - an explorative study of cleaning ladies in Istanbul

Previous research has considered entrepreneurship as a way out of poverty and as a chance to foster economic growth. Moreover, specifically start-ups headed by women have played an important role in the economic development and it has been argued that gender-related issues, amongst others, play a significant role for the performance of a country or region. Against this background, this qualitative study explores desires, reluctances and constraints toward entrepreneurial activities of a comparably homogenous group of potential (poor) entrepreneurs in an emerging economy—cleaning ladies in Istanbul. We focus on this particular context as still rather little is known on reasons why women do not start a business (in Turkey). We believe exploring the reasons why certain individuals choose not to become entrepreneurs is at least as telling as investigating why they do so. We draw upon the social dimensions of entrepreneurship by Shapero and Sokol (1982) alongside Institutional Theory and posit that normative and cognitive forces may shape individual decisions on entrepreneurship. We identified two basic clusters of women and discuss possible hindrance factors undermining entrepreneurial desires and limitations for entrepreneurship as well as possible avenues for policy makers (and MNCs) to foster entrepreneurship in the given community.

Study of individual lactation patterns of Iranian dairy buffaloes

The aims of the current study were 1) to investigate the effects of some environmental factors on lactation curve traits (LCTs) including initial milk yield (A), peak yield (PY), days to attain peak yield (PD), inclining- and declining slope of lactation (B and C, respectively), persistency (Per), and 240-d milk yield, and 2) to estimate pairwise phenotypic correlations between these traits in two Iranian buffalo ecotypes (Khuzestani and Azeri buffaloes). The dataset consisted of 15396 and 9283 lactations from 6632 Khuzestani and 3558 Azeri buffaloes, respectively (collected during 1992–2009). The results revealed that almost all of the factors had significant effects on the majority of the LCTs, whereby age group, parity and season of calving had greater influence on 240-d milk yield and PY than the other LCTs in both of the ecotypes. These effects were more apparent in Khuzestani buffaloes than in Azeri buffaloes. In the Khuzestani ecotype, the LCTs were significantly correlated with each other. However, in the Azeri ecotype the 240-d milk yield showed no significant relationship with parameters B, PD and Per. In conclusion, the studied factors play an important role in determining both the shape of the lactation curve and the overal performance of Iranian dairy buffaloes.

Magnetic interactions between transition metal impurities and clusters mediated by low-dimensional metallic hosts: A first principles theoretical investigation

The magnetic properties and interactions between transition metal (TM) impurities and clusters in low-dimensional metallic hosts are studied using a first principles theoretical method. In the first part of this work, the effect of magnetic order in 3d-5d systems is addressed from the perspective of its influence on the enhancement of the magnetic anisotropy energy (MAE). In the second part, the possibility of using external electric fields (EFs) to control the magnetic properties and interactions between nanoparticles deposited at noble metal surfaces is investigated. The influence of 3d composition and magnetic order on the spin polarization of the substrate and its consequences on the MAE are analyzed for the case of 3d impurities in one- and two-dimensional polarizable hosts. It is shown that the MAE and easy- axis of monoatomic free standing 3d-Pt wires is mainly determined by the atomic spin-orbit (SO) coupling contributions. The competition between ferromagnetic (FM) and antiferromagnetic (AF) order in FePtn wires is studied in detail for n=1-4 as a function of the relative position between Fe atoms. Our results show an oscillatory behavior of the magnetic polarization of Pt atoms as a function of their distance from the magnetic impurities, which can be correlated to a long-ranged magnetic coupling of the Fe atoms. Exceptionally large variations of the induced spin and orbital moments at the Pt atoms are found as a function of concentration and magnetic order. Along with a violation of the third Hund’s rule at the Fe sites, these variations result in a non trivial behavior of the MAE. In the case of TM impurities and dimers at the Cu(111), the effects of surface charging and applied EFs on the magnetic properties and substrate-mediated magnetic interactions have been investigated. The modifications of the surface electronic structure, impurity local moments and magnetic exchange coupling as a result of the EF-induced metallic screening and charge rearrangements are analysed. In a first study, the properties of surface substitutional Co and Fe impurities are investigated as a function of the external charge per surface atom q. At large inter-impurity distances the effective magnetic exchange coupling ∆E between impurities shows RKKY-like oscillations as a function of the distance which are not significantly affected by the considered values of q. For distances r < 10 Å, important modifications in the magnitude of ∆E, involving changes from FM to AF coupling, are found depending non-monotonously on the value and polarity of q. The interaction energies are analysed from a local perspective. In a second study, the interplay between external EF effects, internal magnetic order and substrate-mediated magnetic coupling has been investigated for Mn dimers on Cu(111). Our calculations show that EF (∼ 1eV/Å) can induce a switching from AF to FM ground-state magnetic order within single Mn dimers. The relative coupling between a pair of dimers also shows RKKY-like oscillations as a function of the inter-dimer distance. Their effective magnetic exchange interaction is found to depend significantly on the magnetic order within the Mn dimers and on their relative orientation on the surface. The dependence of the substrate-mediated interaction on the magnetic state of the dimers is qualitatively explained in terms of the differences in the scattering of surface electrons. At short inter-dimer distances, the ground-state configuration is determined by an interplay between exchange interactions and EF effects. These results demonstrate that external surface charging and applied EFs offer remarkable possibilities of manipulating the sign and strength of the magnetic coupling of surface supported nanoparticles.

Individual Decision-Making and Inflation Persistence

The traditional task of a central bank is to preserve price stability and, in doing so, not to impair the real economy more than necessary. To meet this challenge, it is of great relevance whether inflation is only driven by inflation expectations and the current output gap or whether it is, in addition, influenced by past inflation. In the former case, as described by the New Keynesian Phillips curve, the central bank can immediately and simultaneously achieve price stability and equilibrium output, the so-called ‘divine coincidence’ (Blanchard and Galí 2007). In the latter case, the achievement of price stability is costly in terms of output and will be pursued over several periods. Similarly, it is important to distinguish this latter case, which describes ‘intrinsic’ inflation persistence, from that of ‘extrinsic’ inflation persistence, where the sluggishness of inflation is not a ‘structural’ feature of the economy but merely ‘inherited’ from the sluggishness of the other driving forces, inflation expectations and output. ‘Extrinsic’ inflation persistence is usually considered to be the less challenging case, as policy-makers are supposed to fight against the persistence in the driving forces, especially to reduce the stickiness of inflation expectations by a credible monetary policy, in order to reestablish the ‘divine coincidence’. The scope of this dissertation is to contribute to the vast literature and ongoing discussion on inflation persistence: Chapter 1 describes the policy consequences of inflation persistence and summarizes the empirical and theoretical literature. Chapter 2 compares two models of staggered price setting, one with a fixed two-period duration and the other with a stochastic duration of prices. I show that in an economy with a timeless optimizing central bank the model with the two-period alternating price-setting (for most parameter values) leads to more persistent inflation than the model with stochastic price duration. This result amends earlier work by Kiley (2002) who found that the model with stochastic price duration generates more persistent inflation in response to an exogenous monetary shock. Chapter 3 extends the two-period alternating price-setting model to the case of 3- and 4-period price durations. This results in a more complex Phillips curve with a negative impact of past inflation on current inflation. As simulations show, this multi-period Phillips curve generates a too low degree of autocorrelation and too early turnings points of inflation and is outperformed by a simple Hybrid Phillips curve. Chapter 4 starts from the critique of Driscoll and Holden (2003) on the relative real-wage model of Fuhrer and Moore (1995). While taking the critique seriously that Fuhrer and Moore’s model will collapse to a much simpler one without intrinsic inflation persistence if one takes their arguments literally, I extend the model by a term for inequality aversion. This model extension is not only in line with experimental evidence but results in a Hybrid Phillips curve with inflation persistence that is observably equivalent to that presented by Fuhrer and Moore (1995). In chapter 5, I present a model that especially allows to study the relationship between fairness attitudes and time preference (impatience). In the model, two individuals take decisions in two subsequent periods. In period 1, both individuals are endowed with resources and are able to donate a share of their resources to the other individual. In period 2, the two individuals might join in a common production after having bargained on the split of its output. The size of the production output depends on the relative share of resources at the end of period 1 as the human capital of the individuals, which is built by means of their resources, cannot fully be substituted one against each other. Therefore, it might be rational for a well-endowed individual in period 1 to act in a seemingly ‘fair’ manner and to donate own resources to its poorer counterpart. This decision also depends on the individuals’ impatience which is induced by the small but positive probability that production is not possible in period 2. As a general result, the individuals in the model economy are more likely to behave in a ‘fair’ manner, i.e., to donate resources to the other individual, the lower their own impatience and the higher the productivity of the other individual. As the (seemingly) ‘fair’ behavior is modelled as an endogenous outcome and as it is related to the aspect of time preference, the presented framework might help to further integrate behavioral economics and macroeconomics.