X-ray absorption spectroscopy of FeH to aid its identification in astrochemical environments.

We present the first absorption spectrum of the unperturbed diatomic molecular ion FeH in any wavelength range. The cryogenic X-ray absorption spectrum at the L and L edge is consistent with an iron 3d occupation of 6.24e.

Symmetry reduction induced by argon tagging gives access to low-lying excited states of FeH in the overtone region of the Fe-H stretching mode.

Iron is the most abundant transition metal in the interstellar medium (ISM), and is thought to be involved in a variety of astrochemical processes. Here, we present the infrared multiple photon dissociation (IRMPD) spectra of ArFeH and their deuterated isotopologues in the region of 2240-14 000 cm. The Fe-H overtone stretching mode in ArFeH and ArFeH is observed at 3636 ± 28 cm and 3659 ± 13 cm, respectively.

Master equation modeling of water dissociation in small ionic water clusters: Ag(HO) , = 4-6.

We model temperature-dependent blackbody infrared radiative dissociation (BIRD) rate coefficients of Ag(HO) , = 4-6, a system with loosely bound water molecules. We employ a master equation modeling (MEM) approach with consideration of absorption and emission of blackbody radiation, comparing single and multiple-well descriptions. The unimolecular dissociation rate coefficients are obtained using the Rice-Ramsperger-Kassel-Marcus (RRKM) theory, employing two approaches to model the sum of states in the transition state, the rigid activated complex (RAC) and the phase space limit (PSL) approach.

Multiconfigurational Character of Repulsive AΣ State Leaves Strong Signature in the Photodissociation Spectrum of Zn.

For the excitation to a repulsive state of a diatomic molecule, one expects a single broad peak in the photodissociation spectrum. For Zn, however, two peaks for the spin- and symmetry-allowed AΣ ← XΣ transition are observed. A detailed quantum-chemical analysis reveals pronounced multiconfigurational character of the AΣ state.

Master equation modeling of blackbody infrared radiative dissociation (BIRD) of hydrated peroxycarbonate radical anions.

Molecular cluster ions, which are stored in an electromagnetic trap under ultra-high vacuum conditions, undergo blackbody infrared radiative dissociation (BIRD). This process can be simulated with master equation modeling (MEM), predicting temperature-dependent dissociation rate constants, which are very sensitive to the dissociation energy. We have recently introduced a multiple-well approach for master equation modeling, where several low-lying isomers are taken into account.

Magic cluster sizes of cationic and anionic sodium chloride clusters explained by statistical modeling of the complete phase space.

As one of the main components of sea salt aerosols, sodium chloride is involved in numerous atmospheric processes. Gas-phase clusters are ideal models to study fundamental physical and chemical properties of sodium chloride, which are significantly affected by the cluster size. Of particular interest are magic cluster sizes, which exhibit high intensities in mass spectra.

Iron Complexes as Potential Carriers of Diffuse Interstellar Bands: The Photodissociation Spectrum of Fe(HO) at Optical Wavelengths.

The fullerene ion C is the only carrier of diffuse interstellar bands (DIBs) identified so far. Transition-metal compounds feature electronic transitions in the visible and near-infrared regions, making them potential DIB carriers. Since iron is the most abundant transition metal in the cosmos, we here test this idea with Fe(HO).

Secondary retensioning of a tether-based device for transapical transcatheter mitral valve implantation.

Objectives: Relevant paravalvular leakage (PVL) due to prosthesis dislodgement is a rare but potentially severe complication after transcatheter mitral valve implantation (TMVI). Due to the epicardial anchoring mechanism of the Tendyne® TMVI system, repositioning of the valve stent may be possible by retensioning of the tether. This multicentre study aimed to investigate the procedural and short-term safety as well as efficacy of retensioning manoeuvres.

Spectroscopy of cluster aerosol models: IR and UV spectra of hydrated glyoxylate with and without sea salt.

Glyoxylic acid is formed in the troposphere by oxidation of organic molecules. In sea salt aerosols, it is expected to be present as glyoxylate, integrated into the salt environment and strongly interacting with water molecules. In water, glyoxylate is in equilibrium with its -diol form.

A laboratory-based multifunctional near ambient pressure X-ray photoelectron spectroscopy system for electrochemical, catalytic, and cryogenic studies.

A versatile multifunctional laboratory-based near ambient pressure x-ray photoelectron spectroscopy (XPS) instrument is presented. The entire device is highly customized regarding geometry, exchangeable manipulators and sample stages for liquid- and solid-state electrochemistry, cryochemistry, and heterogeneous catalysis. It therefore delivers novel and unique access to a variety of experimental approaches toward a broad choice of functional materials and their specific surface processes.

Overview article: Impact of primary and secondary care collaboration on hospitalization for chronic heart failure: Two comparative studies.

Introduction: In the past decade, a legal framework was created in Germany that promotes intense collaboration at the interface between primary and secondary care. This overview article distinguishes between the effects of two complementary programs aimed at improving ambulatory care in Baden-Wuerttemberg: (1) general practitioner-centered care (GPCC), which strengthens the role of general practitioners, and (2) collaborative cardiology care (CCC), which coordinates primary and cardiology care.

Methods: The overview article presents two already published studies that assess the impact of the programs on hospitalizations in patients with chronic heart failure (CHF) based on claims data from 2016.

Collaborative Ambulatory Orthopaedic Care in Patients with Hip and Knee Osteoarthritis: A Retrospective Comparative Cohort Study on Health Utilisation and Economic Outcomes.

Objective: To evaluate a novel healthcare programme for the treatment of patients with hip and knee osteoarthritis in southern Germany in terms of clinical and health economic outcomes. The study is based on claims data from 2014 to 2017.

Methods: We conducted a retrospective comparative cohort study of 9768 patients with hip and knee osteoarthritis, of whom 9231 were enrolled in a collaborative ambulatory orthopaedic care programme (intervention group), and 537 patients received usual orthopaedic care (control group).

Carbon Dioxide and Water Activation by Niobium Trioxide Anions in the Gas Phase.

Transition metals are important in various industrial applications including catalysis. Due to the current concentration of CO in the atmosphere, various ways for its capture and utilization are investigated. Here, we study the activation of CO and HO at [NbO] in the gas phase using a combination of infrared multiple photon dissociation spectroscopy and density functional theory calculations.

Cusp overlap versus standard three-cusp technique for self-expanding Evolut transcatheter aortic valves.

Background: Reducing rates of permanent pacemaker implantation (PPI) after transcatheter aortic valve implantation (TAVI) is important for achieving the best procedural outcomes. The cusp overlap technique (COT) implements procedural steps including an overlap angulation of the right and left coronary cusp to mitigate this complication.

Aims: We investigated the incidence of PPI and complication rates following the COT compared to the standard three-cusp implantation technique (3CT) in an all-comers cohort.

Surface or Internal Hydration - Does It Really Matter?

The precise location of an ion or electron, whether it is internally solvated or residing on the surface of a water cluster, remains an intriguing question. Subtle differences in the hydrogen bonding network may lead to a preference for one or the other. Here we discuss spectroscopic probes of the structure of gas-phase hydrated ions in combination with quantum chemistry, as well as H/D exchange as a means of structure elucidation.

Thermally Activated vs. Photochemical Hydrogen Evolution Reactions-A Tale of Three Metals.

Molecular processes behind hydrogen evolution reactions can be quite complex. In macroscopic electrochemical cells, it is extremely difficult to elucidate and understand their mechanism. Gas phase models, consisting of a metal ion and a small number of water molecules, provide unique opportunities to understand the reaction pathways in great detail.

Simplified Multiple-Well Approach for the Master Equation Modeling of Blackbody Infrared Radiative Dissociation of Hydrated Carbonate Radical Anions.

Blackbody infrared radiative dissociation (BIRD) in a collision-free environment is a powerful method for the experimental determination of bond dissociation energies. In this work, we investigate temperature-dependent BIRD of CO(HO) at 250-330 K to determine water binding energies and assess the influence of multiple isomers on the dissociation kinetics. The ions are trapped in a Fourier-transform ion cyclotron resonance mass spectrometer, mass selected, and their BIRD kinetics are recorded at varying temperatures.

Strength of Safety Measures Introduced by Medical Practices to Prevent a Recurrence of Patient Safety Incidents: An Observational Study.

Objective: The aim of this study was to analyze the strength of safety measures described in incident reports in outpatient care.

Methods: An incident reporting project in German outpatient care included 184 medical practices with differing fields of specialization. The practices were invited to submit anonymous incident reports to the project team 3 times for 17 months.

Differences in opioid prescription rates between patients with musculoskeletal disorders enrolled in coordinated ambulatory healthcare and patients receiving usual care: a retrospective observational cohort study.

Objectives: To compare opioid prescription rates between patients enrolled in coordinated ambulatory care and patients receiving usual care.

Design: In this retrospective cohort study, we analysed claims data for insured patients with non-specific/specific back pain or osteoarthritis of hip or knee from 2014 to 2017.

Setting: The study was based on administrative data provided by the statutory health insurance fund 'Allgemeine Ortskrankenkasse', in the state of Baden-Wurttemberg, Germany.

Evaluation of a collaborative ambulatory orthopedic care program for patients with hip and knee osteoarthritis: a comparative observational cohort study.

Background: In 2014, the novel orthopedic care program was established by the AOK health insurance fund in southern Germany to improve ambulatory care for patients with musculoskeletal disorders. The program offers extended consultation times, structured collaboration between general practitioners and specialists, as well as a renewed focus on guideline-recommended therapies and patient empowerment. The aim of this study was to assess the impact of the program on health service utilization in patients with hip and knee osteoarthritis (OA).

Decomposition of Halogenated Molybdenum Sulfide Dianions [MoSX] (X = Cl, Br, I).

Molybdenum sulfides are considered a promising and inexpensive alternative to platinum as a catalyst for the hydrogen evolution reaction. In this study, we perform collision-induced dissociation experiments in the gas phase with the halogenated molybdenum sulfides [MoSCl], [MoSBr], and [MoSI]. We show that the first fragmentation step for all three dianions is charge separation via loss of a halide ion.

Rearrangement and decomposition pathways of bare and hydrogenated molybdenum oxysulfides in the gas phase.

Molybdenum sulfides and molybdenum oxysulfides are considered a promising and cheap alternative to platinum as a catalyst for the hydrogen evolution reaction (HER). To better understand possible rearrangements during catalyst activation, we perform collision induced dissociation experiments in the gas phase with eight different molybdenum oxysulfides, namely [MoOS], [MoOS], [MoOS], [MoOS], [MoOS], [HMoOS], [HMoOS] and [HMoOS], on a Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometer. We identify fragmentation channels of the molybdenum oxysulfides and their interconnections.

Toward Detection of FeH in the Interstellar Medium: Infrared Multiple Photon Dissociation Spectroscopy of ArFeH.

The iron hydride molecular cation FeH is expected to be present in the interstellar medium. Because of the lack of laboratory data, it is yet to be identified in spectrally resolved astronomic observations. As a benchmark for computational predictions and to guide an experimental search for the ro-vibrational lines of FeH, we performed infrared multiple photon dissociation (IRMPD) spectroscopy of FeH tagged with two argon atoms.