The application of electronic structure methods to complex chemical systems : novel reaction mechanisms and photochemical phenomena

The work provided throughout this thesis focuses on the appropriate application of electronic structure methods to provide chemical and photochemical insights over a range of systems of significantly differing size. Density functional theory (DFT) is utilised to investigate the presence of aromatic character in heteroatomic and multiheteroatomic compounds using nucleus independent chemical shift methods (chapter 2), linking these properties to both the atypical behaviour of 1,3,2,4- dioxazaboroles and the presence of aromatic character in non-planar phosphorous containing rings. The reactive and mechanistic chemistry of 1,3,2,4-dioxazaboroles (chapter 3) is analysed to determine the susceptibility of these compounds to the effects of electronic substituents; time-dependent DFT (TD-DFT) is utilised to provide a photochemical characterisation of 1,3,2,4-dioxazaboroles as they pertain to their potential use as sensing materials. DFT analysis of mechanistic chemistry has been extended to large M4L6 cages, focusing on the applicability of a, previously discounted, transition pathway to explain experimental findings concerning the isomerisation of these complexes. Both DFT and TD-DFT are applied to iridium complexes of biochemical interest for uses in photodynamic therapy (chapter 6) in order to characterise energetic, one- and two-photon absorption of these. Finally, high accuracy coupled cluster calculations are applied to Fe(CO)5 (chapter 5) to investigate the one- and two-photon absorption of this complex, along with the excited state potential energy surfaces as a function of axial and equatorial stretching to provide insight into the rapid dissociation of this benchmark inorganic compound

How selective are real wage cuts? : a micro-analysis using linked employer-employee data

Using linked employer–employee panel data for Germany, this paper investigates whether firms implement real wage reductions in a selective manner. In line with insider–outsider and several strands of efficiency wage theory, we find strong evidence for selective wage cuts with high-productivity workers being spared even when controlling for permanent differences in firms’ wage policies. In contrast to some recent contributions stressing fairness considerations, we also find that wage cuts increase wage dispersion among peers rather than narrowing it. Notably, the same selectivity pattern shows up when restricting our analysis to firms covered by collective agreements or having a works council

The Impossibility of a Perfectly Competitive Labor Market

Using the institutional theory of transaction cost, I demonstrate that the assumptions of the competitive labor market model are internally contradictory and lead to the conclusion that on purely theoretical grounds a perfectly competitive labor market is a logical impossibility. By extension, the familiar diagram of wage determination by supply and demand is also a logical impossibility and the neoclassical labor demand curve is not a well-defined construct. The reason is that the perfectly competitive market model presumes zero transaction cost and with zero transaction cost all labor is hired as independent contractors, implying multi-person firms, the employment relationship, and labor market disappear. With positive transaction cost, on the other hand, employment contracts are incomplete and the labor supply curve to the firm is upward sloping, again causing the labor demand curve to be ill-defined. As a result, theory suggests that wage rates are always and everywhere an amalgam of an administered and bargained price. Working Paper 06-0

Protocol for the saMS trial (supportive adjustment for multiple sclerosis): a randomized controlled trial comparing cognitive behavioral therapy to supportive listening for adjustment to multiple sclerosis

BackgroundMultiple Sclerosis (MS) is an incurable, chronic, potentially progressive and unpredictable disease of the central nervous system. The disease produces a range of unpleasant and debilitating symptoms, which can have a profound impact including disrupting activities of daily living, employment, income, relationships, social and leisure activities, and life goals. Adjusting to the illness is therefore particularly challenging. This trial tests the effectiveness of a cognitive behavioural intervention compared to supportive listening to assist adjustment in the early stages of MS.MethodsThis is a two arm randomized multi-centre parallel group controlled trial. 122 consenting participants who meet eligibility criteria will be randomly allocated to receive either Cognitive Behavioral Therapy or Supportive Listening. Eight one hour sessions of therapy (delivered over a period of 10 weeks) will be delivered by general nurses trained in both treatments. Self-report questionnaire data will be collected at baseline (0 weeks), mid-therapy (week 5 of therapy), post-therapy (15 weeks) and at six months (26 weeks) and twelve months (52 weeks) follow-up. Primary outcomes are distress and MS-related social and role impairment at twelve month follow-up. Analysis will also consider predictors and mechanisms of change during therapy. In-depth interviews to examine participants’ experiences of the interventions will be conducted with a purposively sampled sub-set of the trial participants. An economic analysis will also take place. DiscussionThis trial is distinctive in its aims in that it aids adjustment to MS in a broad sense. It is not a treatment specifically for depression. Use of nurses as therapists makes the interventions potentially viable in terms of being rolled out in the NHS. The trial benefits from incorporating patient input in the development and evaluation stages. The trial will provide important information about the efficacy, cost-effectiveness and acceptability of the interventions as well as mechanisms of psychosocial adjustment.Trial registrationCurrent Controlled Trials ISRCTN91377356<br/