114 research outputs found
Simulation of Auger decay dynamics in the hard X-ray regime: HCl as a showcase
Auger decay after photoexcitation or photoemission of an electron from a deep inner shell in the hard X-ray regime can be rather complex, implying a multitude of phenomena such as multiple-step cascades, post-collision interaction (PCI), and electronic state-lifetime interference. Furthermore, in a molecule nuclear motion can also be triggered. Here we discuss a comprehensive theoretical method which allows us to analyze in great detail Auger spectra measured around an inner-shell ionization threshold. HCl photoexcited or photoionized around the deep Cl 1s threshold is chosen as a showcase. Our method allows calculating Auger cross sections considering the nature of the ground, intermediate and final states (bound or dissociative), and the evolution of the relaxation process, including both electron and nuclear dynamics. In particular, we show that we can understand and reproduce a so-called experimental 2D-map, consisting of a series of resonant Auger spectra measured at different photon energies, therefore obtaining a detailed picture of all above-mentioned dynamical phenomena at once
Ultrafast nuclear dynamics in the doubly-core-ionized water molecule observed via Auger spectroscopy
We present a combined experimental and theoretical study of the Auger-emission spectrum following double core ionization and excitation of gas-phase water molecules with hard-x-ray synchrotron radiation above the O K−2 threshold. We observe an indication of ultrafast proton motion occurring within the 1.5 fs lifetime of the double-core-hole (DCH) states in water. Furthermore, we have identified symmetric and antisymmetric dissociation modes characteristic for particular DCH states. Our results serve as a fundamental reference for state-of-the-art studies of DCH dynamic processes in liquid water both at synchrotron and free-electron-laser facilities
Two-to-one Auger decay of a double L vacancy in argon
We have observed L223−M3 Auger decay in argon where a double vacancy is filled
by two valence electrons and a single electron is ejected from the atom. A
well-resolved spectrum of these two-to-one electron transitions is compared to
the result of the second-order perturbation theory and its decay branching
ratio is determined
Subfemtosecond Control of Molecular Fragmentation by Hard X-Ray Photons
Tuning hard x-ray excitation energy along Cl 1s→σ∗ resonance in gaseous HCl
allows manipulating molecular fragmentation in the course of the induced
multistep ultrafast dissociation. The observations are supported by
theoretical modeling, which shows a strong interplay between the topology of
the potential energy curves, involved in the Auger cascades, and the so-called
core-hole clock, which determines the time spent by the system in the very
first step. The asymmetric profile of the fragmentation ratios reflects
different dynamics of nuclear wave packets dependent on the photon energy
Single and multiple excitations in double-core-hole states of free water molecules
We present a combined experimental and theoretical study of the double-core-hole photoelectron spectrum obtained in isolated water molecules irradiated with hard x-rays above the oxygen K−2 threshold. States of the type O K−2V and multiply excited states are created by single-photon absorption and subsequent one-electron emission. A detailed analysis enabled by high experimental resolution reveals dissociative nuclear dynamics in the K−2V pre-edge states. At the binding energies above the K−2 double-ionization potential, a complex spectral pattern is observed and attributed to highly excited states involving multiple shake-up excitation processes with the aid of state-of-the-art theoretical calculations. A strong broadening due to the nuclear motion indicates a highly dissociative nature of these multiply excited states, in agreement with the theoretical analysis
Argon as a showcase
Electronic-state–lifetime interference is a phenomenon specific for ionization
of atoms and molecules in the hard-x-ray regime. Using resonant KL2,3L2,3
Auger decay in argon as a showcase, we present a model that allows extracting
the interference terms directly from the cross sections of the final
electronic states. The analysis provides fundamental information on the
excitation and decay processes such as probabilities of various decay paths
and the values of the dipole matrix elements for transitions to the excited
states. Our results shed light on the interplay between spectator, shake-down,
and shake-up processes in the relaxation of deep core-hole states
From synchrotrons for XFELs : The soft x-ray near-edge spectrum of the ESCA molecule
A predictive understanding of soft x-ray near-edge absorption spectra of small molecules is an enduring theoretical challenge and of current interest for x-ray probes of molecular dynamics. We report the experimental absorption spectrum for the electron spectroscopy for chemical analysis (ESCA) molecule (ethyl trifluoroacetate) near the carbon 1s absorption edge between 285-300 eV. The ESCA molecule with four chemically distinct carbon sites has previously served as a theoretical benchmark for photoelectron spectra and now for photoabsorption spectra. We report a simple edge-specific approach for systematically expanding standard basis sets to properly describe diffuse Rydberg orbitals and the importance of triple excitations in equation-of-motion coupled-cluster calculations of the energy interval between valence and Rydberg excitations
Double-core-hole states in CH3CN: Pre-edge structures and chemical-shift contributions
Spectra reflecting the formation of single-site double-core-hole pre-edge states involving the N 1s and C 1s core levels of acetonitrile have been recorded by means of high-resolution single-channel photoelectron spectroscopy using hard X-ray excitation. The data are interpreted with the aid of ab initio quantum chemical calculations, which take into account the direct or conjugate nature of this type of electronic states. Furthermore, the photoelectron spectra of N 1s and C 1s singly core-ionized states have been measured. From these spectra, the chemical shift between the two C 1s−1 states is estimated. Finally, by utilizing C 1s single and double core-ionization potentials, initial and final state effects for the two inequivalent carbon atoms have been investigated
Covid-19 as a risk factor for repeated cardiovascular events
The purpose of the study is to assess the risk of recurrent cardiovascular events in patients with a history of acute myocardial infarction (AMI) and COVID-19.Цель исследования – оценка риска повторных сердечно-сосудистых событий у пациентов с острым инфарктом миокарда (ОИМ) и COVID-19 в анамнезе
Energy Transfer into Molecular Vibrations and Rotations by Recoil in Inner-Shell Photoemission
A mixture of CF4 and CO gases is used to study photoelectron recoil effects extending into the tender x-ray region. In CF4, the vibrational envelope of the C 1s photoelectron spectrum becomes fully dominated by the recoil-induced excitations, revealing vibrational modes hidden from Franck-Condon excitations. In CO, using CF4 as an accurate energy calibrant, we determine the partitioning of the recoil-induced internal excitation energy between rotational and vibrational excitation. The observed rotational recoil energy is 2.88(28) times larger than the observed vibrational recoil energy, well in excess of the ratio of 2 predicted by the basic recoil model. The experiment is, however, in good agreement with the value of 2.68 if energy transfer via Coriolis coupling is included
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