Identification and classification of shareable tacit knowledge associated with experience in the Chinese software industry sector

The study reported in this thesis aimed to provide an ontology of professional activities in the software industry that require and enable the acquisition of experience and that, in turn, is the basis for tacit knowledge creation. The rationale behind the creation of such an ontology was based on the need to externalise this tacit knowledge and then record such externalisations so that these can be shared and disseminated across organisations through electronic records management. The research problem here is to conciliate highly theoretical principles associated with tacit knowledge and the ill-defined and quasi-colloquial concept of experience into a tool that can be used by more technical and explicit knowledge minded practitioners of electronic records management. The ontology produced and proposed here provides exactly such a bridge, by identifying what aspects of professional and personal experience should be captured and organising these aspects into an explicit classification that can be used to capture the tacit knowledge and codify it into explicit knowledge. Since such ontologies are always closely related to actual contexts of practice, the researcher decided to choose her own national context of China, where she had worked before and had good guarantees of industrial access. This study used a multiple case-study Straussian Grounded Theory inductive approach. Data collection was conducted through semi-structured interviews in order to get direct interaction with practitioners in the field and capture individuals opinions and perceptions, as well as interpret individuals understandings associated with these processes. The interviews were conducted in three different and representative types of company (SMEs, State Owned and Large Private) in an attempt to capture a rich variety of possible contexts in the SW sector in a Chinese context. Data analysis was conducted according to coding the procedures advocated by Grounded Theory, namely: open, axial and selective coding. Data collection and analysis was conducted until the emergent theory reached theoretical saturation. The theory generated identified 218 different codes out of 797 representative quotations. These codes were grouped and organised into a category hierarchy that includes 6 main categories and 31 sub-categories, which are, in turn, represented in the ontology proposed. This emergent theory indicates in a very concise manner that experienced SW development practitioners in China should be able to understand the nature and value of experience in the SW industry, effectively communicate with other stake holders in the SW development process, be able and motivated to actively engage with continuous professional development, be able to share knowledge with peers and the profession at large, effectively work on projects and exhibit a sound professional attitude both internally to their own company and externally to customers, partners and even competitors. This basic theory was then further analysed by applying selective coding. This resulted in a main theory centred on Working in Projects, which was clearly identified as the core activity in the SW Industry reflecting its design and development nature. Directly related with the core category, three other significant categories were identified as enablers: Communication, Knowledge Sharing and Individual Development. Additionally, Understanding the Nature of Experience in the SW Industry and Professional Attitude were identified as drivers for the entire process of reflection, experience acquisition and tacit knowledge construction by the individual practitioners. Finally, as an integral part of any inductive process of research, the final stage in this study was to position the emerged theory in the body of knowledge. This resulted in the understanding that the theory presented in this study bridges two extremely large bodies of literature: employability skills and competencies. Both of these bodies of literature put their emphasis in explicit knowledge concerning skills and competencies that are defined so that they can be measured and assessed. The focus of the theory proposed in this thesis on experience and resulting acquisition of tacit knowledge allows a natural link between the employability skills and competencies in the SW industry that was hitherto lacking in the body of knowledge. The ontology proposed is of interest to academics in the areas of knowledge management, electronic records management and information systems. The same ontology may be of interest to human resources practitioners to select and develop experienced personnel as well as knowledge and information professionals in organisations

Identification of tacit knowledge associated with experience: a Chinese software industry study

This paper reports on a research project that aimed at identifying the professional and personal experience from individuals in the SMEs in the Software (SW) industry sector in China. This study employed an inductive qualitative approach based on a single case study and grounded theory (GT) data analysis. The SW company is a SME that specialises in multimedia SW research and development and is located in Xiamen City (Fujian Province, South of China). Six participants, selected on the basis of their role in SW design and development, were interviewed using a semi‐structured interview script. These in‐depth interviews ranged from 100 to 120 minutes in length. After completing the open coding of the six interview transcripts, the researcher obtained 121 codes and 215 quotations from the interview data. These codes were grouped and organized into a category hierarchy that included 6 main structured categories as the result of axial coding. The results of the study enabled the development of a taxonomy and classification of tacit knowledge related to experience in the different stages of the SW development process. The study also showed that each identified category of tacit knowledge is not necessarily confined to one specific SW development stage or even to a specific role in the process. This emergent theory challenges traditional perceptions that each stage requires very precise types of skills, experience and even types of individuals

Plasmons in Pb nanowire arrays on Si(557): Between one and two dimensions

The plasmon dispersion in arrays of nanowires of Pb close to an average Pb coverage of one monolayer was determined on the Si(557) surface using electron energy loss spectroscopy with both high energy and momentum resolution. While we find purely one-dimensional (1D) plasmon losses at a Pb concentration of 1.31 monolayers (ML), measured with respect to the Si(111) surface concentration, the 1.2 and 1.4 ML coverages exhibit wavelength-dependent transitions from 1D to anisotropic 2D properties. However, due to the high anisotropy in the system at all coverages, the dispersion curves exhibit 1D characteristics in both directions. This behavior seems to be related to the Pb-induced refacetting of the Si(557) surface, which depends on Pb coverage. It changes both effective system sizes and coupling strength between miniterraces. © 2011 American Physical Society.Ministry of Education, Culture, Sports, Science, and Technology, Japa

Wider. Bigger. Greater. Neo-Palladian country houses as representations of power struggle, globalization and "Britishness" in the United Kingdom of the 1750s

Neo-Palladianism in the United Kingdom followed a clear formula when it was first introduced in the 1720s: small and compact villas, a central portico and references to the Villa Emo or La Rotonda. This concept changed significantly till the 1750s: wings were added, the complexes became wider and references became more diverse. The early 18th century was also a time of change for the political and social situation in the United Kingdom. The Hanoverians took over the throne from the Stuarts in 1714 and the Whigs governed the country for almost three decades. At the same time the world had become more global thanks to colonization and Britain was constantly in conflict with continental Europe. This meant that the collective identity of the British elite had to be newly created. This thesis discusses how Neo-Palladian country houses on the English countryside were used to create this new collective identity of the British elite in the 1750s

Substrate-Dependent Two-State Reactivity in Iron-Catalyzed Alkene [2+2] Cycloaddition Reactions

Iron-catalyzed alkene [2+2] cycloaddition reactions represent a promising stepwise pathway to effect the kinetically hindered concerted [2+2] cycloaddition. However, the fundamental reactivity paradigm of these reactions remains unclear. Based on high level combined CASPT2/DFT modelings, herein we reveal an unprecedented substrate-dependent two-state reactivity scenario for the key CC coupling in this iron catalysis, in which the representative substrates of mono-olefins only and mono-olefin plus 1,3-diene exhibit different reactivity paradigms. The role of the redox-active ligand is found to generate a ferric oxidation state for the metallacyclic intermediate of CC coupling, thereby rendering a thermodynamically more accessible Fe^III/Fe^I reductive elimination process compared with the otherwise Fe^II/Fe⁰ one. The enhancement of the spin state transition efficiency between the singlet and triplet states is predicted as an alternative way to increase the CC coupling reactivity in the cross [2+2] cycloaddition reactions between mono-olefins and dienes. This work highlights the ab initio multi-reference method in describing very complicated open-shell iron catalysis

Mechanism of Organophosphonate Catabolism by Diiron Oxygenase PhnZ: A Third Iron-Mediated O–O Activation Scenario in Nature

Diiron oxygenase PhnZ catalyzes the catabolism of organophosphonate (Pn) (<i>R</i>)-2-amino-1-hydroxyethylphosphonic to glycine and inorganic phosphate (Pi). In this Pn catabolism way, PhnZ oxidatively cleaves the highly stable C–P bond in Pn to produce Pi. However, the mechanism of this enzyme that affords aquatic and marine bacteria in Pi-limited environments to utilize the most abundant environmental Pn (2-amino-ethylphosphonic acid) as the source of Pi is still unclear. In this work, extensive QM/MM calculations reveal that the mechanism of PhnZ consists of four consecutive steps: (1) rate-limiting α-H abstraction of Pn by Fe^III-superoxo; (2) formation of Fe^IIIOOC_α peroxide; (3) concerted O insertion into C_α–P bond of Pn initiated by “inverse” heterolytic O–O cleavage; and (4) phosphate hydrolysis to glycine and Pi. Intriguingly, the enzymatic reaction mechanism of PhnZ for the crucial breakage of the C–P bond is characterized by the “inverse” heterolytic O–O cleavage of Fe^IIIOOC_α intermediate, which renders the distal O atom more oxidative to oxygenate Pn than the homolytic O–O cleavage. In this way, PhnZ adopts a mechanism quite different from the related diiron oxygenase MIOX, with His62 residue playing an important role. This unusual “inverse” heterolytic O–O cleavage mode, apart from the well-known homolytic and “normal” heterolytic ones, constitutes a third iron-mediated O–O activation scenario in nature, which is expected to have its broad occurrence in oxidative transformation involving heteroatoms of sulfur and phosphorus

Convergent Theoretical Prediction of Reactive Oxidant Structures in Diiron Arylamine Oxygenases AurF and CmlI: Peroxo or Hydroperoxo?

AurF and CmlI are currently the only two known diiron arylamine oxygenases. On the basis of extensive quantum mechanical/molecular mechanical (QM/MM) spectroscopic and mechanistic modelings, here we predict that the key oxygenated intermediates in AurF and CmlI, so-called <b>P</b>, are uniformly hydroperoxo species having similar structures. As a basis for mechanistic unification in AurF and CmlI, the proposed diferric-hydroperoxo <b>P</b> is calculated to be able to promote the arylamine N-oxygenation with highly accessible kinetics. This convergent μ-η⁰:η² structural assignment of <b>P</b>’s in AurF and CmlI can rationalize many conundrums for <b>P</b>, including the different Mössbauer spectroscopic parameters, low O–O vibrational frequency, ambiphilic reactivity, and inertness toward C–H activation. In view of the very limited knowledge about hydroperoxo species in diiron enzymes, the novel diferric-hydroperoxo-mediated N-oxygenation mechanism revealed in this work opens up a new avenue for understanding the O₂ activation mode in nature. For elucidating the structures of transient oxidants for diiron enzymes, the promising approach of QM/MM Mössbauer spectroscopic modeling is highlighted as a key problem solver in mechanistic enzymatic research

Performance of Density Functionals for Activation Energies of Re-Catalyzed Organic Reactions

By employing high-level coupled cluster CCSD­(T)-F12 calculations as reference, we herein systematically assessed the performance of 16 popular density functional theory (DFT) approximations for typical rhenium-catalyzed reactions. The reactions under study cover those catalyzed by low-valent rhenium­(I)/(III) carbonyl complexes as well as high-valent organorhenium­(VII) bisperoxo complex. Without DFT dispersion correction, the four best-performing functionals for the barrier heights are B2GP-PLYP, TPSSh, B3LYP, and PBE0 with the mean unsigned deviations (MUDs) under 1.6 kcal/mol. Among these four functionals, B2GP-PLYP generates more accurate barrier heights, while B3LYP and TPSSh behave more reliably in the barrier trend description for these Re-catalyzed reactions. In general, herein the hybrid functionals are better choices than pure GGA or pure meta-GGA functionals. DFT empirical dispersion corrections were found to have beneficial effects on MUDs only for four tested functionals of BMK, CAM-B3LYP, LC-ωPBE, and ωB97X. Often associated with very large errors up to about 15 kcal/mol in barrier height for many tested functionals, the reaction catalyzed by high-valent rhenium­(VII) bisperoxo is apparently different from the ones catalyzed by low-valent rhenium­(I)/(III) carbonyl complexes. For reactions catalyzed by Re­(I)/(III) carbonyl complexes, ωB97XD with dispersion correction performs excellently (MUD = 0.63 kcal/mol) and hence is highly recommended for these Re­(I)/Re­(III)-mediated reactions

Assessment of DFT Methods for Computing Activation Energies of Mo/W-Mediated Reactions

Using high level ab initio coupled cluster calculations as reference, the performances of 15 commonly used density functionals (DFs) on activation energy calculations for typical Mo/W-mediated reactions have been systematically assessed for the first time in this work. The selected representative Mo/W-mediated reactions cover a wide range from enzymatic reactions to organometallic reactions, which include Mo-catalyzed aldehyde oxidation (aldehyde oxidoreductase), Mo-catalyzed dimethyl sulfoxide (DMSO) reduction (DMSO reductase), W-catalyzed acetylene hydration (acetylene hydratase), Mo/W-mediated olefin metathesis, Mo/W-mediated olefin epoxidation, W-mediated alkyne metathesis, and W-mediated C–H bond activation. Covering both Mo- and W-mediated reactions, four DFs of B2GP-PLYP, M06, B2-PLYP, and B3LYP are uniformly recommended with and without DFT empirical dispersion correction. Among these four DFs, B3LYP is notably improved in performance by DFT empirical dispersion correction. In addition to the absolute value of calculation error, if the trend of DFT results is also a consideration, B2GP-PLYP, B2-PLYP, and M06 keep better performance than other functionals tested and constitute our final recommendation of DFs for both Mo- and W-mediated reactions

Performance of Density Functionals for Activation Energies of Zr-Mediated Reactions

Coupled cluster CCSD­(T) calculations with core–valence correlation and complete basis set (CBS) limit extrapolation are used to benchmark the performance of commonly used density functionals in computing energy barriers for Zr-mediated reactions involving zirconocene species. These reactions include (a) insertions of the Zr–H bond of Cp₂Zr­(H)Cl into CC, CC, and CO bonds and (b) C–H activations by ZrN bond in Cp₂ZrNH. The best performing functionals are M06-L, M06, and M06-2X in the M06 series, all having mean unsigned deviations (MUD) less than 2 kcal/mol. The worst performing functional is OLYP, with a distinctly large MUD of more than 10 kcal/mol. Considering also the trends in barrier heights and the systematic barrier height deviation, our best recommended functional is M06-2X. In this work, DFT empirical dispersion correction (DFT-D3) is found to improve the performance of barrier height values for most functionals (especially of OLYP and B3LYP). With DFT empirical dispersion correction, we also recommend M06-2X for reaction barrier calculations of Zr-mediated reactions