Direct detection of atmospheric particle formation using the Neutral cluster and Air Ion Spectrometer

Aerosol particles play an important role in the Earth s atmosphere and in the climate system: they scatter and absorb solar radiation, facilitate chemical processes, and serve as seeds for cloud formation. Secondary new particle formation (NPF) is a globally important source of these particles. Currently, the mechanisms of particle formation and the vapors participating in this process are, however, not truly understood. In order to fully explain atmospheric NPF and subsequent growth, we need to measure directly the very initial steps of the formation processes. This thesis investigates the possibility to study atmospheric particle formation using a recently developed Neutral cluster and Air Ion Spectrometer (NAIS). First, the NAIS was calibrated and intercompared, and found to be in good agreement with the reference instruments both in the laboratory and in the field. It was concluded that NAIS can be reliably used to measure small atmospheric ions and particles directly at the sizes where NPF begins. Second, several NAIS systems were deployed simultaneously at 12 European measurement sites to quantify the spatial and temporal distribution of particle formation events. The sites represented a variety of geographical and atmospheric conditions. The NPF events were detected using NAIS systems at all of the sites during the year-long measurement period. Various particle formation characteristics, such as formation and growth rates, were used as indicators of the relevant processes and participating compounds in the initial formation. In a case of parallel ion and neutral cluster measurements, we also estimated the relative contribution of ion-induced and neutral nucleation to the total particle formation. At most sites, the particle growth rate increased with the increasing particle size indicating that different condensing vapors are participating in the growth of different-sized particles. The results suggest that, in addition to sulfuric acid, organic vapors contribute to the initial steps of NPF and to the subsequent growth, not just later steps of the particle growth. As a significant new result, we found out that the total particle formation rate varied much more between the different sites than the formation rate of charged particles. The results infer that the ion-induced nucleation has a minor contribution to particle formation in the boundary layer in most of the environments. These results give tools to better quantify the aerosol source provided by secondary NPF in various environments. The particle formation characteristics determined in this thesis can be used in global models to assess NPF s climatic effects.

Novel Approaches to the Sampling of Atmospheric Aerosols and Determination of Chemical Composition

The Earth s climate is a highly dynamic and complex system in which atmospheric aerosols have been increasingly recognized to play a key role. Aerosol particles affect the climate through a multitude of processes, directly by absorbing and reflecting radiation and indirectly by changing the properties of clouds. Because of the complexity, quantification of the effects of aerosols continues to be a highly uncertain science. Better understanding of the effects of aerosols requires more information on aerosol chemistry. Before the determination of aerosol chemical composition by the various available analytical techniques, aerosol particles must be reliably sampled and prepared. Indeed, sampling is one of the most challenging steps in aerosol studies, since all available sampling techniques harbor drawbacks. In this study, novel methodologies were developed for sampling and determination of the chemical composition of atmospheric aerosols. In the particle-into-liquid sampler (PILS), aerosol particles grow in saturated water vapor with further impaction and dissolution in liquid water. Once in water, the aerosol sample can then be transported and analyzed by various off-line or on-line techniques. In this study, PILS was modified and the sampling procedure was optimized to obtain less altered aerosol samples with good time resolution. A combination of denuders with different coatings was tested to adsorb gas phase compounds before PILS. Mixtures of water with alcohols were introduced to increase the solubility of aerosols. Minimum sampling time required was determined by collecting samples off-line every hour and proceeding with liquid-liquid extraction (LLE) and analysis by gas chromatography-mass spectrometry (GC-MS). The laboriousness of LLE followed by GC-MS analysis next prompted an evaluation of solid-phase extraction (SPE) for the extraction of aldehydes and acids in aerosol samples. These two compound groups are thought to be key for aerosol growth. Octadecylsilica, hydrophilic-lipophilic balance (HLB), and mixed phase anion exchange (MAX) were tested as extraction materials. MAX proved to be efficient for acids, but no tested material offered sufficient adsorption for aldehydes. Thus, PILS samples were extracted only with MAX to guarantee good results for organic acids determined by liquid chromatography-mass spectrometry (HPLC-MS). On-line coupling of SPE with HPLC-MS is relatively easy, and here on-line coupling of PILS with HPLC-MS through the SPE trap produced some interesting data on relevant acids in atmospheric aerosol samples. A completely different approach to aerosol sampling, namely, differential mobility analyzer (DMA)-assisted filter sampling, was employed in this study to provide information about the size dependent chemical composition of aerosols and understanding of the processes driving aerosol growth from nano-size clusters to climatically relevant particles (>40 nm). The DMA was set to sample particles with diameters of 50, 40, and 30 nm and aerosols were collected on teflon or quartz fiber filters. To clarify the gas-phase contribution, zero gas-phase samples were collected by switching off the DMA every other 15 minutes. Gas-phase compounds were adsorbed equally well on both types of filter, and were found to contribute significantly to the total compound mass. Gas-phase adsorption is especially significant during the collection of nanometer-size aerosols and needs always to be taken into account. Other aims of this study were to determine the oxidation products of β-caryophyllene (the major sesquiterpene in boreal forest) in aerosol particles. Since reference compounds are needed for verification of the accuracy of analytical measurements, three oxidation products of β-caryophyllene were synthesized: β-caryophyllene aldehyde, β-nocaryophyllene aldehyde, and β-caryophyllinic acid. All three were identified for the first time in ambient aerosol samples, at relatively high concentrations, and their contribution to the aerosol mass (and probably growth) was concluded to be significant. Methodological and instrumental developments presented in this work enable fuller understanding of the processes behind biogenic aerosol formation and provide new tools for more precise determination of biosphere-atmosphere interactions.

Optical Tweezers for Single Molecule Biology

Molecular machinery on the micro-scale, believed to be the fundamental building blocks of life, involve forces of 1-100 pN and movements of nanometers to micrometers. Micromechanical single-molecule experiments seek to understand the physics of nucleic acids, molecular motors, and other biological systems through direct measurement of forces and displacements. Optical tweezers are a popular choice among several complementary techniques for sensitive force-spectroscopy in the field of single molecule biology. The main objective of this thesis was to design and construct an optical tweezers instrument capable of investigating the physics of molecular motors and mechanisms of protein/nucleic-acid interactions on the single-molecule level. A double-trap optical tweezers instrument incorporating acousto-optic trap-steering, two independent detection channels, and a real-time digital controller was built. A numerical simulation and a theoretical study was performed to assess the signal-to-noise ratio in a constant-force molecular motor stepping experiment. Real-time feedback control of optical tweezers was explored in three studies. Position-clamping was implemented and compared to theoretical models using both proportional and predictive control. A force-clamp was implemented and tested with a DNA-tether in presence of the enzyme lambda exonuclease. The results of the study indicate that the presented models describing signal-to-noise ratio in constant-force experiments and feedback control experiments in optical tweezers agree well with experimental data. The effective trap stiffness can be increased by an order of magnitude using the presented position-clamping method. The force-clamp can be used for constant-force experiments, and the results from a proof-of-principle experiment, in which the enzyme lambda exonuclease converts double-stranded DNA to single-stranded DNA, agree with previous research. The main objective of the thesis was thus achieved. The developed instrument and presented results on feedback control serve as a stepping stone for future contributions to the growing field of single molecule biology.

Magnetically induced currents and magnetic response properties of molecules

The magnetically induced currents in organic monoring and multiring molecules, in Möbius shaped molecules and in inorganic all-metal molecules have been investigated by means of the Gauge-including magnetically induced currents (GIMIC) method. With the GIMIC method, the ring-current strengths and the ring-current density distributions can be calculated. For open-shell molecules, also the spin current can be obtained. The ring-current pathways and ring-current strengths can be used to understand the magnetic resonance properties of the molecules, to indirectly identify the effect of non-bonded interactions on NMR chemical shifts, to design new molecules with tailored properties and to discuss molecular aromaticity. In the thesis, the magnetic criterion for aromaticity has been adopted. According to this, a molecule which has a net diatropic ring current might be aromatic. Similarly, a molecule which has a net paratropic current might be antiaromatic. If the net current is zero, the molecule is nonaromatic. The electronic structure of the investigated molecules has been resolved by quantum chemical methods. The magnetically induced currents have been calculated with the GIMIC method at the density-functional theory (DFT) level, as well as at the self-consistent field Hartree-Fock (SCF-HF), at the Møller-Plesset perturbation theory of the second order (MP2) and at the coupled-cluster singles and doubles (CCSD) levels of theory. For closed-shell molecules, accurate ring-current strengths can be obtained with a reasonable computational cost at the DFT level and with rather small basis sets. For open-shell molecules, it is shown that correlated methods such as MP2 and CCSD might be needed to obtain reliable charge and spin currents. The basis set convergence has to be checked for open-shell molecules by performing calculations with large enough basis sets. The results discussed in the thesis have been published in eight papers. In addition, some previously unpublished results on the ring currents in the endohedral fullerene Sc3C2@C80 and in coronene are presented. It is shown that dynamical effects should be taken into account when modelling magnetic resonance parameters of endohedral metallofullerenes such as Sc3C2@C80. The ring-current strengths in a series of nano-sized hydrocarbon rings are related to static polarizabilities and to H-1 nuclear magnetic resonance (NMR) shieldings. In a case study on the possible aromaticity of a Möbius-shaped [16]annulene we found that, according to the magnetic criterion, the molecule is nonaromatic. The applicability of the GIMIC method to assign the aromatic character of molecules was confirmed in a study on the ring currents in simple monocylic aromatic, homoaromatic, antiaromatic, and nonaromatic hydrocarbons. Case studies on nanorings, hexaphyrins and [n]cycloparaphenylenes show that explicit calculations are needed to unravel the ring-current delocalization pathways in complex multiring molecules. The open-shell implementation of GIMIC was applied in studies on the charge currents and the spin currents in single-ring and bi-ring molecules with open shells. The aromaticity predictions that are made based on the GIMIC results are compared to other aromaticity criteria such as H-1 NMR shieldings and shifts, electric polarizabilities, bond-length alternation, as well as to predictions provided by the traditional Hückel (4n+2) rule and its more recent extensions that account for Möbius twisted molecules and for molecules with open shells.

A kinetic Ising model study of dynamical correlations in confined fluids: Emergence of both fast and slow time scales

Experiments and computer simulation studies have revealed existence of rich dynamics in the orientational relaxation of molecules in confined systems such as water in reverse micelles, cyclodextrin cavities, and nanotubes. Here we introduce a novel finite length one dimensional Ising model to investigate the propagation and the annihilation of dynamical correlations in finite systems and to understand the intriguing shortening of the orientational relaxation time that has been reported for small sized reverse micelles. In our finite sized model, the two spins at the two end cells are oriented in the opposite directions to mimic the effects of surface that in real system fixes water orientation in the opposite directions. This produces opposite polarizations to propagate inside from the surface and to produce bulklike condition at the center. This model can be solved analytically for short chains. For long chains, we solve the model numerically with Glauber spin flip dynamics (and also with Metropolis single-spin flip Monte Carlo algorithm). We show that model nicely reproduces many of the features observed in experiments. Due to the destructive interference among correlations that propagate from the surface to the core, one of the rotational relaxation time components decays faster than the bulk. In general, the relaxation of spins is nonexponential due to the interplay between various interactions. In the limit of strong coupling between the spins or in the limit of low temperature, the nature of relaxation of the spins undergoes a qualitative change with the emergence of a homogeneous dynamics where decay is predominantly exponential, again in agreement with experiments. (C) 2010 American Institute of Physics. doi: 10.1063/1.3474948]

Helsingin metropolialueen maisemaekologiset muutokset vuosina 1955-2009

Landscape is shaped by natural environment and increasingly by human activity. In landscape ecology, the concept of landscape can be defined as a kilometre-scale mosaic formed by different land-use types. In Helsinki Metropolitan Region, the landscape change caused by urbanization has accelerated after the 1950s. Prior to that, the landscape of the region was mainly only shaped by agriculture. The goal of this study was in addition to describing the landscape change to discuss the factors impacting the landscape change and evaluate thelandscape ecological impacts of the change. Three study areas at different distances from Helsinki city centre were chosen in order to look at the landscape change. Study areas were Malmi, Espoo and Mäntsälä regions representing different parts of the urban-to-rural gradient in 1955, 1975, 1990 and 2009. Land-use of the maps was then digitized into five classes: agricultural lands, semi-natural grasslands, built areas, waters and others using GIS methods. First, landscape change was studied using landscape ecological indices. Indices used were PLAND i.e. the proportions of the different land-use types in the landscape; MPS, SHEI and SHDI which describe fragmentation and heterogeneity of the landscape; and MSI and ED which are measures of patch shape. Second, landscape change was studied statistically in relation to topography, soil and urban structure of the study areas. Indicators used concerning urban structure were number of residents, car ownership and travel-related zones of urban form which indicate the degree of urban sprawl within the study areas. For the statistical analyses, each of the 9.25 x 9.25 km sized study areas was further divided into grids with resolution of 0.25 x 0.25 kilometres. Third, the changes in the green structure of the study areas were evaluated. The landscape change reflected by the proportions of the land-use types was the most notable in Malmi area where a large amount of agricultural land was developed from 1955 to 2009. The proportion of semi-natural grasslands also showed an interesting pattern in relation to urbanization. When urbanization started, a great number of agricultural lands were abandoned and turned into semi-natural grasslands but as the urbanization accelerated, the number of semi-natural grasslands started to decline because of urban densification. Landscape fragmentation and heterogeneity were the most widespread in Espoo study area which is not only because of the great differences in relative heights within the region but also its location in the rural-urban fringe. According to the results, urbanization induced agricultural lands to be more regular in shape both spatially and temporally whereas for built areas and semi-natural grasslands the impact of urbanization was reverse. Changes in landscape were the most insignificant in the most rural study area Mäntsälä. In Mäntsälä, built area per resident showed the greatest values indicating a widespread urban sprawl. The values were the smallest in highly urbanized Malmi study area. Unlike other study areas, in Mäntsälä the proportion of developing land in the ecologically disadvantageous cardependent zone was on the increase. On the other hand, the green structure of the Mäntsälä study area was the most advantageous whereas Malmi study area showed the most ecologically disadvantageous structure. Considering all the landscape ecological criteria used, the landscape structure of Espoo study area proved to be the best not least because of the great heterogeneity of its landscape. Thus the study confirmed the previous results according to which landscape heterogeneity is the most significant in areas exposed to a moderate human impact.

Neoarchean sanukitoid series in the Karelian Province, Finland

Sanukitoid series intrusions can be found throughout the Archean Karelian Province of the Fennoscandian shield. All sanukitoids share the same controversial elemental characteristics: they have high content of incompatible elements such as K, Ba, and Sr as well as high content of the compatible elements Mg, Cr, and Ni, and high Mg#. This composition is explained by an enriched mantle wedge origin in a Neoarchean subduction setting. This study concentrates on sanukitoid intrusions and tonalite-trondhjemite-granodiorite series (TTGs) from Finnish part of the Karelian Province. The collected rock samples have been studied in the field and under microscope as well as for their whole-rock (including isotopes) and mineral compositions. The new data together with previously published analyses help us to better understand the petrogenesis, tectonic setting and reworking of the Archean rock units. TTGs from the Karelian Province form a voluminous series of granitoids and reworked migmatites. This study divides TTG series into two subgroups based on their elemental composition: low-HREE (heavy rare earth element) TTGs and high-HREE TTGs indicating pressure differences in their source. Sanukitoid series is a minor, divergent group of intrusions. These intrusions are variable sized, and the texture varies from even-grained to K-feldspar porphyritic. The elemental composition differentiates sanukitoids from more voluminous TTG groups, the SiO2 in sanukitoids varies to include series of gabbro, diorite, and granodiorite. U Pb age determinations from sanukitoid series show temporally limited emplacement between ~ 2745 2715 Ma after the main crust forming period in the area. Hafnium, neodymium, common lead, and oxygene isotopes indicate well homogenized characteristics. Recycled crust has made a variable, yet minor, contribution to sanukitoids, as evidenced by oxygene isotopes and inherited zircon cores. A proposed tectonic setting for the formation of the sanukitoid series is slab breakoff of oceanic lithosphere in subduction setting, with sanukitoids deriving from an enriched mantle wedge. The proposed setting explains some of the peculiar features of sanukitoids, such as their temporally limited occurrence and controversial elemental composition. Sanukitoids would occur after cessation of the regional growth of Archean crust, and they could be derived from mantle wedge previously enriched by melts and fluids from oceanic crust and sediments. A subsequent event during the Paleoproterozoic Svecofennian orogeny at ~1.9 Ga affected the appearance and microstructures of the rocks as well as caused redistribution of lead between minerals and whole rock. However, the deformation was not able to obliterate the original geochemical characteristics of these sanukitoids.

Heating values of mature trees.

The effective heating values of the above and below ground biomass components of mature Scots pine (Pinus sylvestris), Norway spruce (Picea abies), downy birch (Betula pubescens), silver birch (Betula pendula), grey alder (Alnus incana), black alder (Alnus glutinosa) and trembling aspen (Populus tremula) were studied. Each sample tree was divided into wood, bark and foliage components. Bomb calorimetry was used to determine the calorimetric heating values. The species is a significant factor in the heating value of individual tree components. The heating value of the wood proper is highest in conifers. Broad-leaved species have a higher heating value of bark than conifers. The species factor diminishes when the weighted heating value of crown, whole stems or stump-root-system are considered. The crown material has a higher heating value per unit weight in comparison with fuelwood from small-sized stems or wholetrees. The additional advantages of coniferous crown material are that it is a non-industrial biomass resource and is readily available. The variability of both the chemical composition and the heating value is small in any given tree component of any species. However, lignin, carbohydrate and extractive content were found to vary from one part of the tree to another and to correlate with the heating value.

Exact path-integral evaluation of the heat distribution function of a trapped Brownian oscillator

Using path integrals, we derive an exact expression-valid at all times t-for the distribution P(Q,t) of the heat fluctuations Q of a Brownian particle trapped in a stationary harmonic well. We find that P(Q, t) can be expressed in terms of a modified Bessel function of zeroth order that in the limit t > infinity exactly recovers the heat distribution function obtained recently by Imparato et al. Phys. Rev. E 76, 050101(R) (2007)] from the approximate solution to a Fokker-Planck equation. This long-time result is in very good agreement with experimental measurements carried out by the same group on the heat effects produced by single micron-sized polystyrene beads in a stationary optical trap. An earlier exact calculation of the heat distribution function of a trapped particle moving at a constant speed v was carried out by van Zon and Cohen Phys. Rev. E 69, 056121 (2004)]; however, this calculation does not provide an expression for P(Q, t) itself, but only its Fourier transform (which cannot be analytically inverted), nor can it be used to obtain P(Q, t) for the case v=0.

Some observations of tip-vortex cavitation

Cavitation has been observed in the trailing vortex system of an elliptic planform hydrofoil. A complex dependence on Reynolds number and gas content is noted at inception. Some of the observations can be related to tension effects associated with the lack of sufficiently large-sized nuclei. Inception measurements are compared with estimates of pressure in the vortex obtained from LDV measurements of velocity within the vortex. It is concluded that a complete correlation is not possible without knowledge of the fluctuating levels of pressure in tip-vortex flows. When cavitation is fully developed, the observed tip-vortex trajectory shows a surprising lack of dependence on any of the physical parameters varied, such as angle of attack, Reynolds number, cavitation number, and dissolved gas content.

Metsän erirakenteisuutta edistävien hakkuiden kannattavuustarkastelu metsäaluetasolla

Tutkimuksessa vertailtiin metsän erirakenteisuutta edistävien poimintahakkuiden ja pienaukkohakkuiden kannattavuutta metsänhoitosuositusten mukaiseen metsänkasvatukseen Keski-Suomessa. Poimintahakkuut ja pienaukkohakkuut ovat menetelmiä, joilla voidaan lisätä luonnonmetsän häiriödynamiikan mukaista pienipiirteistä elinympäristöjen vaihtelua ja siksi ne sopivat etenkin erityiskohteisiin monimuotoisuuden, maiseman tai metsien monikäytön vuoksi. Ne johtavat yleensä vähitellen eri-ikäisrakenteiseen metsään, jossa puuston läpimittaluokkajakauma muistuttaa käänteistä J-kirjainta. Eri-ikäisrakenteisen metsänkäsittelyn taloudellista kannattavuutta puoltavat uudistumiskustannusten poisjäänti ja tukkipuihin painottuvat säännöllisin väliajoin toteutuvat hakkuut. Menetelmän soveltumista Suomen olosuhteisiin pidetään kuitenkin epävarmana. Tässä tutkimuksessa tarkasteltiin tasaikäisrakenteisen metsän muuttamista eri-ikäisrakenteiseksi 40 vuoden siirtymäaikana Metsähallituksen hallinnoimassa Isojäven ympäristöarvometsässä Kuhmoisissa. Tutkimusaineisto koostui 405 kuusivaltaisesta tasaikäisestä kuviosta, joiden pinta-alasta metsämaata on 636 hehtaaria. Metsän kehitystä simuloitiin puutason kasvumalleja käyttäen ja käsittelytoimenpiteet simuloitiin viisivuotiskausittain SIMO-metsäsuunnitteluohjelmistolla. Simulointien avulla selvitettiin jokaisen käsittelyskenaarion hakkuumäärät puutavaralajeittain, diskontatut kassavirrat ja puustopääoman muutos tarkasteluajanjakson aikana. Puunkorjuun yksikkökustannusten laskennan apuna käytettiin automatisoitua seurantajärjestelmää, jossa metsäkoneisiin asennettuilla matkapuhelimilla kerättiin MobiDoc2-sovelluksella metsäkoneiden käytöstä kiihtyvyystiedot, GPS-paikkatiedot ja syötetiedot. Lopulta jokaiselle käsittelyskenaariolle laskettiin metsän puuntuotannollista arvoa kuvaavalla tuottoarvon yhtälöllä nettonykyarvot, josta vähennettiin diskontatut puunkorjuun kustannukset. Tutkimuksen tulosten mukaan poimintahakkuun NPV oli 3 prosentin korkokannalla noin 91 % (7420 €/ha) ja pienaukkohakkuiden noin 99 % (8076 €/ha) metsänhoitosuositusten mukaisesta käsittelystä (8176 €/ha). Komparatiivinen statiikka osoitti, että korkokannan kasvattaminen 5 prosenttiin ei olennaisesti lisännyt nettonykyarvojen eroja. Poimintahakkuiden puunkorjuun yksikkökustannukset olivat 0,8 €/m3 harvennushakkuita pienemmät ja 7,2 €/m3 uudistushakkuita suuremmat. Pienaukkohakkuiden yksikkökustannukset olivat 0,7 €/m3 uudistushakkuita suuremmat.Tulosten perusteella on väistämätöntä että siirtymävaihe tasaikäisrakenteisesta eri-ikäisrakenteiseksi metsäksi aiheuttaa taloudellisia tappioita siitäkin huolimatta, että hakkuut ovat voimakkaita ja tehdään varttuneeseen kasvatusmetsään. Tappion määrä on metsän peitteisyyden ylläpidosta aiheutuva vaihtoehtoiskustannus.

Nonlinear Transport in Hybrid Polypyrrole-Gold Nanostructures

We have studied charge transport in nanometer scale films of polypyrrole (PPy) that were grown electrochemically onto discontinuous ultrathin films of gold. The gold films consisted of 100 nm size islands, separated from each other by nanometer-size gaps. The thickness of PPy can be varied from 30 to 200 nm. The I-V characteristics of these hybrid PPy-Au nanostructures show strong non-linearity at low temperatures, and in particular for the more insulating samples. The hopping transport is further verified from the log / versus V-1/4 plots. Furthermore, the I-V data follow an empirical relation dlog//dV(1/4) similar to T-1/2.

Towards Explaining the Tasks and Roles of the Boards of Directors

While previous research has helped to improve our understanding of corporate governance and boards of directors, less is known about the factors that affect boards’ tasks and roles and directors’ motivation and engagement. This requires knowledge of how board decisions are being made and the internal and external factors that affect the decision-making process. Large inferential leaps have been made from board demographics to firm performance with equivocal results. This thesis concentrates on how the institutional, behavioral and social identification factors impact the enactment of board roles and tasks. Data used in this thesis were collected in 2009 through a mailed survey to Finnish large and middle-sized corporations. The findings suggest that firstly, the national context of an organization is reflected in board roles and shapes how and for what reasons the board roles are carried out; secondly, the directors’ human and external social capital invariably impacts their engagement in board tasks and that conflicts among directors moderate those relationships; finally, directors’ identification with the organization, its shareholders and its customers affect the directors’ involvement in board tasks. By addressing the impact of organisational context, board-internal behaviour and social identification of board members on board roles and tasks, this thesis firstly complements the shareholder supremacy view as the only reason for the board’s involvement with specific tasks; secondly questions the existence of the board as separate from its institutional context; and thirdly questions the view that a board is a ‘black box’, subject to a selection of input demographic variables and producing quantifiable results. The thesis demonstrates that boards are complex organisational bodies, which involve much interaction among board members. Director behaviour and its influence on board decision making is an important determinant of board tasks and boards are likely subjected to inter-group tensions and are susceptible to the influence of internal and external social forces.

Modelling vacuum arcs : from plasma initiation to surface interactions

A better understanding of vacuum arcs is desirable in many of today's 'big science' projects including linear colliders, fusion devices, and satellite systems. For the Compact Linear Collider (CLIC) design, radio-frequency (RF) breakdowns occurring in accelerating cavities influence efficiency optimisation and cost reduction issues. Studying vacuum arcs both theoretically as well as experimentally under well-defined and reproducible direct-current (DC) conditions is the first step towards exploring RF breakdowns. In this thesis, we have studied Cu DC vacuum arcs with a combination of experiments, a particle-in-cell (PIC) model of the arc plasma, and molecular dynamics (MD) simulations of the subsequent surface damaging mechanism. We have also developed the 2D Arc-PIC code and the physics model incorporated in it, especially for the purpose of modelling the plasma initiation in vacuum arcs. Assuming the presence of a field emitter at the cathode initially, we have identified the conditions for plasma formation and have studied the transitions from field emission stage to a fully developed arc. The 'footing' of the plasma is the cathode spot that supplies the arc continuously with particles; the high-density core of the plasma is located above this cathode spot. Our results have shown that once an arc plasma is initiated, and as long as energy is available, the arc is self-maintaining due to the plasma sheath that ensures enhanced field emission and sputtering. The plasma model can already give an estimate on how the time-to-breakdown changes with the neutral evaporation rate, which is yet to be determined by atomistic simulations. Due to the non-linearity of the problem, we have also performed a code-to-code comparison. The reproducibility of plasma behaviour and time-to-breakdown with independent codes increased confidence in the results presented here. Our MD simulations identified high-flux, high-energy ion bombardment as a possible mechanism forming the early-stage surface damage in vacuum arcs. In this mechanism, sputtering occurs mostly in clusters, as a consequence of overlapping heat spikes. Different-sized experimental and simulated craters were found to be self-similar with a crater depth-to-width ratio of about 0.23 (sim) - 0.26 (exp). Experiments, which we carried out to investigate the energy dependence of DC breakdown properties, point at an intrinsic connection between DC and RF scaling laws and suggest the possibility of accumulative effects influencing the field enhancement factor.

Effect of Sorbate-Zeolite Interaction on Cluster Lifetime and Size of Sorbates: Xe in NaY

Molecular dynamics calculations are reported for Xe in sodium Y zeolite with varying strengths of sorbate-zeolite dispersion interaction. In the absence of any dispersion interaction between the sorbate and the zeolite, the presence of the zeolite has a purely geometrical role. Increase in the strength of the sorbate-zeolite interaction increases the monomer population and decreases the population of dimers and higher sized clusters. The lifetime of the monomers as well as dimers increases with the strength of the dispersion interaction. The observed variations in the lifetime and the population of the different sized clusters is explained in terms of the changes in the potential energy surface caused by the increase in the strength of the dispersion interaction.