Completing the triad: Synthesis and full characterization of homoleptic and heteroleptic carbonyl and nitrosyl complexes of the group VI metals

Oxidation of M(CO)$_{6}$ (M = Cr, Mo, W) with the synergistic oxidative system Ag[WCA]/0.5 I$_{2}$ yields the fully characterized metalloradical salts [M(CO)$_{6}$]+˙[WCA]− (weakly coordinating anion WCA = [F-{Al(OR$^{F}$)$_{3}$}$_{2}$]$^{-}$, R$^{F}$ = C(CF$_{3}$)$_{3}$). The new metalloradical cations with M = Mo and W showcase a similar structural fluxionality as the previously reported [Cr(CO)$_{6}$]$^{+}$˙. Their reactivity increases from M = Cr < Mo < W and their syntheses allow for in-depth insights into the properties of the group 6 carbonyl triad. Furthermore, the reaction of NO$^{+}$[WCA]$^{-}$ with neutral carbonyl complexes M(CO)$_{6}$ gives access to the heteroleptic carbonyl/nitrosyl cations [M(CO)$_{5}$(NO)]$^{+}$ as salts of the WCA [Al(ORF)$_{4}$]$^{-}$, the first complete transition metal triad of their kind

Attosecond electron thermalization by laser-driven electron recollision in atoms

Nonsequential multiple ionization of atoms in intense laser fields is initiated by a recollision between an electron, freed by tunneling, and its parent ion. Following recollision, the initial electron shares its energy with several bound electrons. We use a classical model based on rapid electron thermalization to interpret recent experiments. For neon, good agreement with the available data is obtained with an upper bound of 460 attoseconds for the thermalization time.Comment: 5 pages revtex and 4 figures (eps files

State-resolved measurements of single-electron capture in slow Ne7+- and Ne8+-helium collisions

Single-electron capture in collisions of 9 keV x q Ne8+ and Ne7+ ions with He has been studied using cold-target recoil-ion momentum spectroscopy. With an improved apparatus a longitudinal momentum resolution of 0.07 au has been achieved. This momentum component is directly proportional to the difference in the binding energy of the active electron between the final and the initial state. For the first time state- resolved differential cross sections have been determined with respect to the main quantum number, subshell level and spin state of the captured electron. A comparison with recent theoretical results for energy levels in Be-like Ne is given

The Cognitive Symptom Checklist-Work in cancer patients is related with work functioning, fatigue and depressive symptoms: a validation study

The study objectives are to translate the 21-item Cognitive Symptom Checklist-Work (CSC-W21) to Dutch (CSC-W DV) and to validate the CSC-W DV in working cancer patients. The CSC-W21 was cross-culturally translated and adapted to a Dutch version. In this 19-item version, the dichotomous response option was changed to an ordinal five-point scale. A validation study of the CSC-W DV was conducted among cancer patients who had returned to work during or following cancer treatment. Internal consistency (Cronbach's alpha), structural validity (exploratory factor analysis) and construct validity (hypothesis testing) were evaluated. In a cohort of 364 cancer patients, 341 (94 %) completed the CSC-W DV (aged 50.6 +/- 8.6 years, 60 % women). Exploratory factor analysis revealed two subscales 'working memory' and 'executive function'. The internal consistency of the total scale and subscales was high (Cronbach's alpha = 0.93-0.95). Hypothesis testing showed that self-reported cognitive limitations at work were related to work functioning (P <0.001), fatigue (P = 0.001) and depressive symptoms (P <0.001), but not to self-rated health (P = 0.14). The CSC-W DV showed high internal consistency and reasonable construct validity for measuring work-specific cognitive symptoms in cancer patients. The CSC-W DV was associated in expected ways with work functioning, fatigue and depressive symptoms. It is important to enhance knowledge about cognitive symptoms at work in cancer patients, to guide and support cancer patients as good as possible when they are back at work and to improve their work functioning over time

Experiences of learning through collaborative evaluation from a masters programme in professional education

This paper presents findings from a collaborative evaluation project within a masters programme in professional education. The project aimed to increase knowledge of research methodologies and methods through authentic learning where participants worked in partnership with the tutor to evaluate the module which they were studying. The project processes, areas of the course evaluated and the data collection methods are outlined. The findings focus on key themes from evaluating the effectiveness of using a collaborative evaluation approach, including: enhanced student engagement; creativity of the collaborative evaluation approach; equality between the tutor and students; and enhanced research skills. Discussion focuses on the outcomes and effectiveness of the project and tutor reflections on adopting a collaborative approach. This paper highlights lessons from the project relevant to those interested in staff-student partnership approaches and those facilitating postgraduate learning and teaching programmes and educational research courses

Atomic excitation during recollision-free ultrafast multi-electron tunnel ionization

Modern intense ultrafast pulsed lasers generate an electric field of sufficient strength to permit tunnel ionization of the valence electrons in atoms. This process is usually treated as a rapid succession of isolated events, in which the states of the remaining electrons are neglected. Such electronic interactions are predicted to be weak, the exception being recollision excitation and ionization caused by linearly-polarized radiation. In contrast, it has recently been suggested that intense field ionization may be accompanied by a two-stage `shake-up' reaction. Here we report a unique combination of experimental techniques that enables us to accurately measure the tunnel ionization probability for argon exposed to 50 femtosecond laser pulses. Most significantly for the current study, this measurement is independent of the optical focal geometry, equivalent to a homogenous electric field. Furthermore, circularly-polarized radiation negates recollision. The present measurements indicate that tunnel ionization results in simultaneous excitation of one or more remaining electrons through shake-up. From an atomic physics standpoint, it may be possible to induce ionization from specific states, and will influence the development of coherent attosecond XUV radiation sources. Such pulses have vital scientific and economic potential in areas such as high-resolution imaging of in-vivo cells and nanoscale XUV lithography.Comment: 17 pages, 4 figures, original format as accepted by Nature Physic

Collinear helium under periodic driving: stabilization of the asymmetric stretch orbit

The collinear eZe configuration of helium, with the electrons on opposite sides of the nucleus, is studied in the presence of an external electromagnetic (laser or microwave) field. We show that the classically unstable "asymmetric stretch" orbit, on which doubly excited intrashell states of helium with maximum interelectronic angle are anchored, can be stabilized by means of a resonant driving where the frequency of the electromagnetic field equals the frequency of Kepler-like oscillations along the orbit. A static magnetic field, oriented parallel to the oscillating electric field of the driving, can be used to enforce the stability of the configuration with respect to deviations from collinearity. Quantum Floquet calculations within a collinear model of the driven two-electron atom reveal the existence of nondispersive wave packets localized on the stabilized asymmetric stretch orbit, for double excitations corresponding to principal quantum numbers of the order of N > 10.Comment: 13 pages, 12 figure