Electron spectroscopy and dynamics of HBr around the Br 1s-1 threshold

A comprehensive electron spectroscopic study combined with partial electron yield measurements around the Br 1s ionization threshold of HBr at approximately equal to 13.482 keV is reported. In detail, the Br 1s(-1) X-ray absorption spectrum, the 1s(-1) photoelectron spectrum as well as the normal and resonant KLL Auger spectra are presented. Moreover, the L-shell Auger spectra measured with photon energies below and above the Br 1s(-1) ionization energy as well as on top of the Br 1s(-1)sigma* resonance are shown. The latter two Auger spectra represent the second step of the decay cascade subsequent to producing a Br 1s(-1) core hole. The measurements provide information on the electron and nuclear dynamics of deep core-excited states of HBr on the femtosecond timescale. From the different spectra the lifetime broadening of the Br 1s(-1) single core-hole state as well as of the Br(2s(-2),2s(-1)2p(-1),2p(-2)) double core-hole states are extracted and discussed. The slope of the strongly dissociative HBr 2p(-2)sigma* potential energy curve is found to be about -13.60 eV angstrom(-1). The interpretation of the experimental data, and in particular the assignment of the spectral features in the KLL and L-shell Auger spectra, is supported by relativistic calculations for HBr molecule and atomic Br

Generalization of the post-collision interaction effect from gas-phase to solid-state systems demonstrated in thiophene and its polymers

We demonstrate experimentally and theoretically the presence of the post-collision interaction (PCI) effect in sulfur KL2,3L2,3 Auger electron spectra measured in the gas-phase thiophene and in solid-state organic polymers: polythiophene (PT) and poly(3-hexylthiophene-2,5-diyl), commonly known as P3HT. PCI manifests itself through a distortion and a blueshift of the normal Auger S KL2,3L2,3 spectrum when S 1s ionization occurs close to the ionization threshold. Our investigation shows that the PCI-induced shift of the Auger spectra is stronger in the solid-state polymers than in the gas-phase organic molecule. Theoretical modeling within the framework of the eikonal approximation provides good agreement with the experimental observations. In a solid medium, two effects influence the interaction between the photoelectron and the Auger electron. In detail, stronger PCI in the polymers is attributed to the photoelectron scattering in the solid, which overcompensates the polarization screening of electron charges which causes a reduction of the interaction. Our paper demonstrates the general nature of the PCI effect occurring in different media

X-ray induced ultrafast charge transfer in thiophene-based conjugated polymers controlled by core-hole clock spectroscopy

We explore ultrafast charge transfer (CT) resonantly induced by hard X-ray radiation in organic thiophene-based polymers at the sulfur K-edge. A combination of core-hole clock spectroscopy with real-time propagation time-dependent density functional theory simulations gives an insight into the electron dynamics underlying the CT process. Our method provides control over CT by a selective excitation of a specific resonance in the sulfur atom with monochromatic X-ray radiation. Our combined experimental and theoretical investigation establishes that the dominant mechanism of CT in polymer powders and films consists of electron delocalisation along the polymer chain occurring on the low-femtosecond time scale

A von Hamos spectrometer based on highly annealed pyrolytic graphite crystal in tender x-ray domain

We have built an x-ray spectrometer in a von Hamos configuration based on a highly annealed pyrolytic graphite crystal. The spectrometer is designed to measure x-ray emission in the range of 2–5 keV. A spectral resolution E/ΔE of 4000 was achieved by recording the elastic peak of photons issued from the GALAXIES beamline at the SOLEIL synchrotron radiation facility

Dynamics of core-excited ammonia: disentangling fragmentation pathways by complementary spectroscopic methods

Fragmentation dynamics of core-excited isolated ammonia molecules is studied by two different and complementary experimental methods, high-resolution resonant Auger spectroscopy and electron energy-selected Auger electron–photoion coincidence spectroscopy (AEPICO). The combined use of these two techniques allows obtaining information on different dissociation patterns, in particular fragmentation before relaxation, often called ultrafast dissociation (UFD), and fragmentation after relaxation. The resonant Auger spectra contain the spectral signature of both molecular and fragment final states, and therefore can provide information on all events occurring during the core-hole lifetime, in particular fragmentation before relaxation. Coincidence measurements allow correlating Auger electrons with ionic fragments from the same molecule, and relating the ionic fragments to specific Auger final electronic states, and yield additional information on which final states are dissociative, and which ionic fragments can be produced in timescales either corresponding to the core-hole lifetime or longer. Furthermore, we show that by the combined use of two complementary experimental techniques we are able to identify more electronic states of the NH2+ fragment with respect to the single one already reported in the literature

Impact of opioid-free analgesia on pain severity and patient satisfaction after discharge from surgery: multispecialty, prospective cohort study in 25 countries

Background: Balancing opioid stewardship and the need for adequate analgesia following discharge after surgery is challenging. This study aimed to compare the outcomes for patients discharged with opioid versus opioid-free analgesia after common surgical procedures.Methods: This international, multicentre, prospective cohort study collected data from patients undergoing common acute and elective general surgical, urological, gynaecological, and orthopaedic procedures. The primary outcomes were patient-reported time in severe pain measured on a numerical analogue scale from 0 to 100% and patient-reported satisfaction with pain relief during the first week following discharge. Data were collected by in-hospital chart review and patient telephone interview 1 week after discharge.Results: The study recruited 4273 patients from 144 centres in 25 countries; 1311 patients (30.7%) were prescribed opioid analgesia at discharge. Patients reported being in severe pain for 10 (i.q.r. 1-30)% of the first week after discharge and rated satisfaction with analgesia as 90 (i.q.r. 80-100) of 100. After adjustment for confounders, opioid analgesia on discharge was independently associated with increased pain severity (risk ratio 1.52, 95% c.i. 1.31 to 1.76; P < 0.001) and re-presentation to healthcare providers owing to side-effects of medication (OR 2.38, 95% c.i. 1.36 to 4.17; P = 0.004), but not with satisfaction with analgesia (beta coefficient 0.92, 95% c.i. -1.52 to 3.36; P = 0.468) compared with opioid-free analgesia. Although opioid prescribing varied greatly between high-income and low- and middle-income countries, patient-reported outcomes did not.Conclusion: Opioid analgesia prescription on surgical discharge is associated with a higher risk of re-presentation owing to side-effects of medication and increased patient-reported pain, but not with changes in patient-reported satisfaction. Opioid-free discharge analgesia should be adopted routinely

Développement d'un détecteur sans temps mort sensible en temps et en position : Application à l'étude des collisions de petits agrégats d'argon Ar+n sur une cible d'argon

The aim of this work is the development of a fast multi-hit position and time sensitive detector with zero dead-time for heavy particles in the keV energy range. This new type of detector makes use of a micro-channel plates MCP assembly and combines a detection based on delay line anode with a simultaneous particle imaging provided by CCD-camera. The time pickup accuracy is enhanced by digitalizing the MCP biasing signal. This detector, operating at kHz repetition rate, allows a position resolution better than 100 µm and a time resolution better than 100 ps to be achieved.We have studied the fragmentation induced by collision of small ionic argon clusters (Ar2+ and Ar3+) with an atomic argon target at keV energies range. All the fragmentation channels: collision induced dissociation (CID) and dissociative charge transfer (DCT) have been analysed by the method of vectorial correlation of all the fragments detected in coincidence. The importance of electronic processes in these collision systems is demonstrated through various results. The dependence of the electron transfer on the initial internal energy of the cluster has been stressed out. Ar3+ has been found to be mainly formed of a strongly bound Ar2+ core surrounded by loosely linked Ar atom.Nous avons développé un nouveau système de détection sans temps mort, résolu en temps et en position et basé sur des galettes de microcanaux. Le principe de ce détecteur est de coupler deux systèmes de détection indépendants qui observent le même événement pour aboutir à leur localisation sans temps mort. Le premier système est constitué d'une caméra CCD capable de fournir l'information position. Le deuxième est constitué d'une carte de numérisation pour enregistrer le signal temps issu des galettes de microcanaux. Le lien entre ces deux systèmes est assuré par une anode constituée de deux lignes à retard, placées derrière les galettes de microcanaux, capable de fournir les deux informations temps et position mais d'une façon moins précise. Ce détecteur opérant au kHz permet d'atteindre une résolution spatiale de 100 µm et temporelle de 100 ps.Nous avons étudié la fragmentation induite par collision des petits agrégats d'argon (Ar2+ et Ar3+) avec une cible d'argon atomique dans la gamme des énergies du keV. Toutes les voies de fragmentation : la dissociation induite par collision (CID) et l'échange de charge dissociatif (DCT) sont analysées par la corrélation vectorielle de tous les fragments détectés en coïncidence. En particulier, nous avons montré que le processus DCT dépendait fortement de l'énergie interne initiale de l'agrégat (i.e. du défaut de résonance). La comparaison de diverses observables mesurées en collision Ar2+-Ar et Ar3+-Ar nous a conduit à conclure que les agrégats Ar3+ produits dans notre source ont majoritairement la structure d'un dimère chargé (Ar2+) autour duquel orbite un troisième atome peu lié

Développement d'un détecteur sans temps mort sensible en temps et en position (application à l'étude des collisions de petits agrégats d'argon Ar+n sur une cible d'argon)

Nous avons développé un nouveau système de détection sans temps mort, résolu en temps et en position et basé sur des galettes de microcanaux. Le principe de ce détecteur est de coupler deux systèmes de détection indépendants qui observent le même événement pour aboutir à leur localisation sans temps mort. Le premier système est constitué d'une caméra CCD capable de fournir l'information position. Le deuxième est constitué d'une carte de numérisation pour enregistrer le signal temps issu des galettes de microcanaux. Le lien entre ces deux systèmes est assuré par une anode constituée de deux lignes à retard, placées derrière les galettes de microcanaux, capable de fournir les deux informations temps et position mais d'une façon moins précise. Ce détecteur opérant au kHz permet d'atteindre une résolution spatiale de 100 m et temporelle de 100 ps.Nous avons étudié la fragmentation induite par collision des petits agrégats d'argon (Ar2+ et Ar3+) avec une cible d'argon atomique dans la gamme des énergies du keV. Toutes les voies de fragmentation : la dissociation induite par collision (CID) et l'échange de charge dissociatif (DCT) sont analysées par la corrélation vectorielle de tous les fragments détectés en coïncidence. En particulier, nous avons montré que le processus DCT dépendait fortement de l'énergie interne initiale de l'agrégat (i.e. du défaut de résonance). La comparaison de diverses observables mesurées en collision Ar2+-Ar et Ar3+-Ar nous a conduit à conclure que les agrégats Ar3+ produits dans notre source ont majoritairement la structure d'un dimère chargé (Ar2+) autour duquel orbite un troisième atome peu lié.The aim of this work is the development of a fast multi-hit position and time sensitive detector with zero dead-time for heavy particles in the keV energy range. This new type of detector makes use of a micro-channel plates MCP assembly and combines a detection based on delay line anode with a simultaneous particle imaging provided by CCD-camera. The time pickup accuracy is enhanced by digitalizing the MCP biasing signal. This detector, operating at kHz repetition rate, allows a position resolution better than 100 m and a time resolution better than 100 ps to be achieved.We have studied the fragmentation induced by collision of small ionic argon clusters (Ar2+ and Ar3+) with an atomic argon target at keV energies range. All the fragmentation channels: collision induced dissociation (CID) and dissociative charge transfer (DCT) have been analysed by the method of vectorial correlation of all the fragments detected in coincidence. The importance of electronic processes in these collision systems is demonstrated through various results. The dependence of the electron transfer on the initial internal energy of the cluster has been stressed out. Ar3+ has been found to be mainly formed of a strongly bound Ar2+ core surrounded by loosely linked Ar atom.ORSAY-PARIS 11-BU Sciences (914712101) / SudocSudocFranceF

Time and position sensitive photon detector for coincidence measurements in the keV energy range

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