Reconstruction of the time-dependent electronic wave packet arising from molecular autoionization

Autoionizing resonances are paradigmatic examples of two-path wave interferences between direct photoionization, which takes a few attoseconds, and ionization via quasi-bound states, which takes much longer. Time-resolving the evolution of these interferences has been a long-standing goal, achieved recently in the helium atom owing to progress in attosecond technologies. However, already for the hydrogen molecule, similar time imaging has remained beyond reach due to the complex interplay between fast nuclear and electronic motions. We show how vibrationally resolved photoelectron spectra of H2 allow one to reconstruct the associated subfemtosecond autoionization dynamics by using the ultrafast nuclear dynamics as an internal clock, thus forgoing ultrashort pulses. Our procedure should be general for autoionization dynamics in molecules containing light nuclei, which are ubiquitous in chemistry and biologyThis work was supported by European Research Council advanced grant 290853-XCHEM within the seventh framework program of the European Union. We also acknowledge the financial support from MINECO projects FIS2013-42002-R and FIS2016-77889-R, and the European COST (Cooperation in Science and Technology) Action XLIC CM1204, and the computer time from the Centro de Computación Científica de la Universidad Autónoma de Madrid and Marenostrum Supercomputer Center. A.P. acknowledges a Ramón y Cajal contract from the Ministerio de Economía y Competitividad (Spain). F.M. acknowledges support from the “Severo Ochoa” Programme for Centres of Excellence in R&D (MINECO, grant SEV-2016-0686) and the “María de Maeztu” Programme for Units of Excellence in R&D (MDM-2014-0377). S.E.C. acknowledges funding from the Helmoltz Recognition Award. The Extreme Light Infrastructure Attosecond Light Pulse Source project (GINOP-2.3.6-15-2015-00001) was financed by the European Union and cofinanced by the European Regional Development Fun

Isolating attosecond electron dynamics in molecules where nuclei move fast

Capturing electronic dynamics in real time has been the ultimate goal of attosecond science since its beginning. While for atomic targets the existing measurement techniques have been thoroughly validated, in molecules there are open questions due to the inevitable copresence of moving nuclei, which are not always mere spectators of the phototriggered electron dynamics. Previous work has shown that not only can nuclear motion affect the way electrons move in a molecule, but it can also lead to contradictory interpretations depending on the chosen experimental approach. In this Letter we investigate how nuclear motion affects and eventually distorts the electronic dynamics measured by using two of the most popular attosecond techniques, reconstruction of attosecond beating by interference of two-photon transitions and attosecond streaking. Both methods are employed, in combination with ab initio theoretical calculations, to retrieve photoionization delays in the dissociative ionization of H2, H2 → H+ + H + E -, in the region of the Q1 series of autoionizing states, where nuclear motion plays a prominent role. We find that the experimental reconstruction of attosecond beating by interference of two-photon transitions results are very sensitive to bond softening around the Q1 threshold (27.8 eV), even at relatively low infrared (IR) intensity (I0 ∼ 1.4 × 1011 W/cm2), due to the long duration of the probe pulse that is inherent to this technique. Streaking, on the other hand, seems to be a better choice to isolate attosecond electron dynamics, since shorter pulses can be used, thus reducing the role of bond softening. This conclusion is supported by very good agreement between our streaking measurements and the results of accurate theoretical calculations. Additionally, the streaking technique offers the necessary energy resolution to accurately retrieve the fast-oscillating phase of the photoionization matrix elements, an essential requirement for extending this technique to even more complicated molecular target

Reconstruction of the time-dependent electronic wave packet arising from molecular autoionization

The time evolution of an electronic molecular wave packet is determined using nuclear motion as an internal clock of the system

A molecular clock for autoionization decay

The ultrafast decay of highly excited electronic states is resolved with a molecular clock technique, using the vibrational motion associated to the ionic bound states as a time-reference. We demonstrate the validity of the method in the context of autoionization of the hydrogen molecule, where nearly exact full dimensional ab-initio calculations are available. The vibrationally resolved photoionization spectrum provides a time-energy mapping of the autoionization process into the bound states that is used to fully reconstruct the decay in time. A resolution of a fraction of the vibrational period is achieved. Since no assumptions are made on the underlying coupled electron-nuclear dynamics, the reconstruction procedure can be applied to describe the general problem of the decay of highly excited states in other molecular targetsWe acknowledge the financial support from the FP7 Marie Curie ITN CORINF, the European Research Council under the ERC grant 290853 XCHEM, the European COST Action CM1204 XLIC and the MINECO Project No. FIS201342002-R. AP acknowledges Ramón y Cajal Programme from MINECO (Spain). LM acknowledges support from DFG priority programme 1840 QUTIF. Theoretical calculations were obtained at the Mare Nostrum BSC and CCC-UAM computer center

A molecular clock for autoionization decay

The ultrafast decay of highly excited electronic states is resolved with a molecular clock technique, using the vibrational motion associated to the ionic bound states as a time-reference. We demonstrate the validity of the method in the context of autoionization of the hydrogen molecule, where nearly exact full dimensional ab-initio calculations are available. The vibrationally resolved photoionization spectrum provides a time–energy mapping of the autoionization process into the bound states that is used to fully reconstruct the decay in time. A resolution of a fraction of the vibrational period is achieved. Since no assumptions are made on the underlying coupled electron–nuclear dynamics, the reconstruction procedure can be applied to describe the general problem of the decay of highly excited states in other molecular targets

The role of dipole-forbidden autoionizing resonances in non-resonant one-color two-photon single ionization of N2_2

We present an experimental and theoretical energy- and angle-resolved study on the photoionization dynamics of non-resonant one-color two-photon single valence ionization of neutral N$_2$ molecules. Using 9.3 eV photons produced via high harmonic generation and a 3-D momentum imaging spectrometer, we detect the photoelectrons and ions produced from one-color two-photon ionization in coincidence. Photoionization of N$_2$ populates the X $^2\Sigma^+_g$, A $^2\Pi_u$, and B $^2\Sigma^+_u$ ionic states of N$_2^+$, where the photoelectron angular distributions associated with the X $^2\Sigma^+_g$ and A $^2\Pi_u$ states both vary with changes in photoelectron kinetic energy of only a few hundred meV. We attribute the rapid evolution in the photoelectron angular distributions to the excitation and decay of dipole-forbidden autoionizing resonances that belong to series of different symmetries, all of which are members of the Hopfield series, and compete with the direct two-photon single ionization.Comment: 12 pages, 9 figures, 2 table

Imaging the square of the correlated two-electron wave function of a hydrogen molecule

The toolbox for imaging molecules is well-equipped today. Some techniques visualize the geometrical structure, others the electron density or electron orbitals. Molecules are many-body systems for which the correlation between the constituents is decisive and the spatial and the momentum distribution of one electron depends on those of the other electrons and the nuclei. Such correlations have escaped direct observation by imaging techniques so far. Here, we implement an imaging scheme which visualizes correlations between electrons by coincident detection of the reaction fragments after high energy photofragmentation. With this technique, we examine the H2 two-electron wave function in which electron-electron correlation beyond the mean-field level is prominent. We visualize the dependence of the wave function on the internuclear distance. High energy photoelectrons are shown to be a powerful tool for molecular imaging. Our study paves the way for future time resolved correlation imaging at FELs and laser based X-ray sources.This work was funded by the Deutsche Forschungsgemeinschaft, the BMBF, the European Research Council under the European Union Seventh Framework Programme (FP7/2007-2013)/ERC grant agreement 290853 XCHEM, the MINECO projects FIS2013-42002-R and FIS2016-77889-R, and the European COST Action XLIC CM1204. All calculations were performed at the CCC-UAM and Mare Nostrum Supercomputer Centers. We are grateful to the staff of PETRA III for excellent support during the beam time. K.M. and M.M. would like to thank the DFG for support via SFB925/A3. A.K. and V.S. thank the Wilhelm und Else Heraeus-Foundation for support. J.L. would like to thank the DFG for support. S.K. acknowledges support from the European Cluster of Advanced Laser Light Sources (EUCALL) project which has received funding from the European Union’s Horizon 2020 research and innovation programme under grant agreement No 654220. T.W. was supported by the U.S. Department of Energy Basic Energy Sciences under Contract No. DE-AC02-05CH11231. A.P. acknowledges a Ramón y Cajal contract from the Ministerio de Economa y Competitividad. We thank M. LaraAstiaso for providing us with the Hartree–Fock wave functions

Antimicrobial resistance among migrants in Europe: a systematic review and meta-analysis

BACKGROUND: Rates of antimicrobial resistance (AMR) are rising globally and there is concern that increased migration is contributing to the burden of antibiotic resistance in Europe. However, the effect of migration on the burden of AMR in Europe has not yet been comprehensively examined. Therefore, we did a systematic review and meta-analysis to identify and synthesise data for AMR carriage or infection in migrants to Europe to examine differences in patterns of AMR across migrant groups and in different settings. METHODS: For this systematic review and meta-analysis, we searched MEDLINE, Embase, PubMed, and Scopus with no language restrictions from Jan 1, 2000, to Jan 18, 2017, for primary data from observational studies reporting antibacterial resistance in common bacterial pathogens among migrants to 21 European Union-15 and European Economic Area countries. To be eligible for inclusion, studies had to report data on carriage or infection with laboratory-confirmed antibiotic-resistant organisms in migrant populations. We extracted data from eligible studies and assessed quality using piloted, standardised forms. We did not examine drug resistance in tuberculosis and excluded articles solely reporting on this parameter. We also excluded articles in which migrant status was determined by ethnicity, country of birth of participants' parents, or was not defined, and articles in which data were not disaggregated by migrant status. Outcomes were carriage of or infection with antibiotic-resistant organisms. We used random-effects models to calculate the pooled prevalence of each outcome. The study protocol is registered with PROSPERO, number CRD42016043681. FINDINGS: We identified 2274 articles, of which 23 observational studies reporting on antibiotic resistance in 2319 migrants were included. The pooled prevalence of any AMR carriage or AMR infection in migrants was 25·4% (95% CI 19·1-31·8; I2 =98%), including meticillin-resistant Staphylococcus aureus (7·8%, 4·8-10·7; I2 =92%) and antibiotic-resistant Gram-negative bacteria (27·2%, 17·6-36·8; I2 =94%). The pooled prevalence of any AMR carriage or infection was higher in refugees and asylum seekers (33·0%, 18·3-47·6; I2 =98%) than in other migrant groups (6·6%, 1·8-11·3; I2 =92%). The pooled prevalence of antibiotic-resistant organisms was slightly higher in high-migrant community settings (33·1%, 11·1-55·1; I2 =96%) than in migrants in hospitals (24·3%, 16·1-32·6; I2 =98%). We did not find evidence of high rates of transmission of AMR from migrant to host populations. INTERPRETATION: Migrants are exposed to conditions favouring the emergence of drug resistance during transit and in host countries in Europe. Increased antibiotic resistance among refugees and asylum seekers and in high-migrant community settings (such as refugee camps and detention facilities) highlights the need for improved living conditions, access to health care, and initiatives to facilitate detection of and appropriate high-quality treatment for antibiotic-resistant infections during transit and in host countries. Protocols for the prevention and control of infection and for antibiotic surveillance need to be integrated in all aspects of health care, which should be accessible for all migrant groups, and should target determinants of AMR before, during, and after migration. FUNDING: UK National Institute for Health Research Imperial Biomedical Research Centre, Imperial College Healthcare Charity, the Wellcome Trust, and UK National Institute for Health Research Health Protection Research Unit in Healthcare-associated Infections and Antimictobial Resistance at Imperial College London