Photoelectron spectroscopic study of the oxyallyl diradical

The photoelectron spectrum of the oxyallyl (OXA) radical anion has been measured. The radical anion has been generated in the reaction of the atomic oxygen radical anion (O center dot-) with acetone. Three low-lying electronic states of OXA have been observed in the spectrum. Electronic structure calculations have been performed for the triplet states (B-3(2) and B-3(1)) of OXA and the ground doublet state ((2)A(2)) of the radical anion using density, functional theory (DFT). Spectral simulations have been carried out for the triplet statics based on the results of the DFT calculations. The simulation identifies a vibrational progression of the CCC bending mode of the B-3(2) state of OXA in the lower electron binding energy (eBE) portion of the spectrum. On top of the B-3(2) feature, however, the experimental spectrum exhibits additional photoelectron peaks whose angular distribution is distinct from that for the vibronic peaks of the B-3(2) state. Complete active space self-consistent field (CASSCF) method and second-order perturbation theory based on the CASSCF wave function (CASPT2) have been employed to study the lowest singlet state ((1)A(1)) of OXA. The simulation based on the results of these electronic structure calculations establishes that the overlapping peaks represent the vibrational ground level of the (1)A(1) state and its vibrational progression of the CO stretching mode. The A, state is the lowest electronic state of,OXA, and the electron affinity (EA) of OXA is 1.940 +/- 0.010 eV. The B-3(2) state is the first excited state with an electronic term energy of 55 +/- 2 meV. The widths of the vibronic peaks of the (X) over tilde (1)A(1) state are much broader than those of the (a) over tilde B-3(2) state, implying that the (1)A(1) state is indeed a transition state. The CASSCF and CASPT2 calculations suggest that the (1)A(1) state is at a potential maximum along the nuclear coordinate representing disrotatory motion of the two methylene groups, which leads to three-membered-ring formation, i.e., cydopropanone. The simulation of (b) over tilde B-3(1) OXA reproduces the higher eBE portion of the spectrum very well. The term energy of the B-3(1) state is 0.883 +/- 0.012 eV. Photoelectron spectroscopic measurements have also been conducted for the other ion products of the O center dot- reaction with acetone. The photoelectron imaging spectrum of the acetylcarbene (AC) radical anion exhibits a broad, structureless feature, which is assigned to the (X) over tilde (3)A '' state of AC. The ground ((2)A '') and first excited ((2)A') states of the 1-methylvinoxy (1-MVO) radical have been observed in the photoelectron spectrum of the 1-MVO ion, and their vibronic structure has been analyzed.

Can larger cemented femoral components reduce periprosthetic fractures?

Introduction The risk for late periprosthetic fractures is higher in patients treated for a neck of femur fracture compared to those treated for osteoarthritis. It has been hypothesised that osteopenia and consequent decreased stiffness of the proximal femur are responsible for this. We investigated if a femoral component with a bigger body would increase the torque to failure in a biaxially loaded composite sawbone model. Method A biomechanical composite sawbone model was used. Two different body sizes (Exeter 44-1 vs 44-4) of a polished tapered cemented stem were implanted by an experienced surgeon, in 7 sawbones each and loaded at 40 deg/s internal rotation until failure. Torque to fracture and fracture energy were measured using a biaxial materials testing device (Instron 8874). Data are non-parametric and tested with Mann-Whitney U-test. Results The mean torque load to fracture was 154.1 NM (SD 4.4) for the 44-1 stem and 229 NM (SD10.9) for the 44-4 stem (p = 0.01). The mean fracture energy was 9.6 J (SD1.2) for the 44-1 stem and 17.2 J (SD2.0) for the 44-4 stem (p = 0.14). Conclusion the use of a large body polished tapered cemented stem for neck of femur fractures increases the torque to failure in a biomechanical model and therefore is likely to reduce late periprosthetic fracture risk in this vulnerable cohort.

The Impact of Internal Market Orientation on Staff Service Behaviours

The impact of service direction, service training and staff behaviours on perceptions of service delivery are examined. The impact of managerial behaviour in the form of internal market orientation (IMO) on the attitudes of frontline staff towards the firm and its consequent influence on their customer oriented behaviours is also examined. Frontline service staff working in the consumer transport industry were surveyed to provide subjective data about the constructs of interest in this study, and the data were analysed using structural equations modelling employing partial least squares estimation. The data indicate significant relationships between internal market orientation (IMO), the attitudes of the employees to the firm and their consequent behaviour towards customers. Customer orientation, service direction and service training are all identified as antecedents to high levels of service delivery. The study contributes to marketing theory by providing quantitative evidence to support assumptions that internal marketing has an impact on services success. For marketing practitioners, the research findings offer additional information about the management, training and motivation of service staff towards service excellence.

Measuring internal market orientation

Internal marketing has been discussed in the management and academic literature for over three decades, yet it remains ill defined and poorly operationalized. This paper responds to calls for research to develop a single clear understanding of the construct, for the development of a suitable instrument to measure it, and for empirical evidence of its impact. Existing, divergent conceptualization of internal marketing are explored, and a new, multidimensional construct, describing the managerial behaviors associated with internal marketing is developed, and termed internal market orientation (IMO). IMO represents the adaptation of market orientation to the context of employer-employee exchanges in the internal market. The paper describes the development of a valid and reliable measure of IMO in a retail services context. Five dimensions of IMO are identified and confirmed. These are 1) formal written information generation, 2) formal face-to-face information generation, 3) informal information generation, 4) communication and dissemination of information, and 5) responding to this internal market information. The impact of IMO on important organizational factors is also explored. Results indicate positive consequences for customer satisfaction, relative competitive position, staff attitudes, staff retention and staff compliance.

The impact of internal and external market orientations on firm performance.

The role of internal marketing in developing organisational competencies is identified as a key area for continued research (Rafiq and Ahmed, 2003). One competence of particular interest to marketers is market orientation. This paper examines the impact of internal marketing, operationalised as a set of internal market orientated behaviours (IMO) on market orientation (MO), and consequently organisational performance, and provides the first quantitative evidence to support the long held assumption that internal marketing has an impact on marketing success. Data from UK retail managers were analysed using structural equations modelling employing LISREL software. These data indicate significant relationships between internal market orientation, employee motivation and external marketing success (market orientation, financial performance and customer satisfaction). Our results also support previous findings indicating a positive impact of external market orientation on customer satisfaction and financial performance. For marketing practitioners, the role of internal market orientation is developing marketing strategies is discussed.

Project team’s internal and external social networks and their influence on project performance

The research on project learning has recognised the significance of knowledge transfer in project based organisations (PBOs). Effective knowledge transfer across projects avoids reinventions, enhances knowledge creation and saves lots of time that is crucial in project environment. In order to facilitate knowledge transfer, many PBOs have invested lots of financial and human resources to implement IT-based knowledge repository. However, some empirical studies found that employees would rather turn for knowledge to colleagues despite their ready access to IT-based knowledge repository. Therefore, it is apparent that social networks play a pivotal role in the knowledge transfer across projects. Some scholars attempt to explore the effect of network structure on knowledge transfer and performance, however, focused only on egocentric networks and the groups’ internal social networks. It has been found that the project’s external social network is also critical, in that the team members can not handle critical situations and accomplish the projects on time without the assistance and knowledge from external sources. To date, the influence of the structure of a project team’s internal and external social networks on project performance, and the interrelation between both networks are barely known. In order to obtain such knowledge, this paper explores the interrelation between the structure of a project team’s internal and external social networks, and their effect on the project team’s performance. Data is gathered through survey questionnaire distributed online to respondents. Collected data is analysed applying social network analysis (SNA) tools and SPSS. The theoretical contribution of this paper is the knowledge of the interrelation between the structure of a project team’s internal and external social networks and their influence on the project team’s performance. The practical contribution lies in the guideline to be proposed for constructing the structure of project team’s internal and external social networks.