Laser excitation of the 1-2 transition in singly-ionized helium.

Laser spectroscopy of atomic hydrogen and hydrogen-like atoms is a powerful tool for tests of fundamental physics. The 1-2 transition of hydrogen in particular is a cornerstone for stringent Quantum Electrodynamics (QED) tests and for an accurate determination of the Rydberg constant. We report laser excitation of the 1-2 transition in singly-ionized helium (He), a hydrogen-like ion with much higher sensitivity to QED than hydrogen itself.

Vibronic Correlations in Molecular Strong-Field Dynamics.

We investigate the ultrafast vibronic dynamics triggered by intense femtosecond infrared pulses in small molecules. Our study is based on numerical simulations performed with 2D model molecules and analyzed in the perspective of the renowned Lochfrass and bond-softening models. We give a new interpretation of the observed nuclear wave packet dynamics with a focus on the phase of the bond oscillations.

Production of positronium chloride: A study of the charge exchange reaction between Ps and Cl.

We present cross sections for the formation of positronium chloride (PsCl) in its ground state from the charge exchange between positronium (Ps) and chloride (Cl-) in the range of 10 meV-100 eV Ps energy. We have used theoretical models based on the first Born approximation in its three-body formulation. We simulated the collisions between Ps and Cl- using ab initio binding energies and positronic wave functions at both the mean-field and correlated levels extrapolated to the complete basis set limit.

Alternative Pathway to Double-Core-Hole States.

Excited double-core-hole states of isolated water molecules resulting from the sequential absorption of two x-ray photons have been investigated. These states are formed through an alternative pathway, where the initial step of core ionization is accompanied by the shake-up of a valence electron, leading to the same final states as in the core-ionization followed by core-excitation pathway. The capability of the x-ray free-electron laser to deliver very intense, very short, and tunable light pulses is fully exploited to identify the two different pathways.

Unraveling the variational breakdown of core valence separation calculations: Diagnostic and cure to the over relaxation error of double core hole states.

The core valence separation (CVS) approximation is the most employed strategy to prevent the variational collapse of standard wave function optimization when attempting to compute electronic states bearing one or more electronic vacancies in core orbitals. Here, we explore the spurious consequences of this approximation on the properties of the computed core hole states. We especially focus on the less studied case of double core hole (DCH) states, whose spectroscopic interest has recently been rapidly growing.

Necrotizing fasciitis of the thigh due to a secondary aortoduodenal fistula.

Secondary aortoenteric fistula is an iatrogenic complication after aortic reconstructive surgery presenting with gastrointestinal bleeding and/or infectious symptoms. Infrequently, it may manifest with nonspecific and atypical clinical signs. We present a case of necrotizing fasciitis of the thigh complicating secondary aortoduodenal fistula, diagnosed with CT-scan.

Anisotropic dynamics of two-photon ionization: An attosecond movie of photoemission.

Imaging in real time the complete dynamics of a process as fundamental as photoemission has long been out of reach because of the difficulty of combining attosecond temporal resolution with fine spectral and angular resolutions. Here, we achieve full decoding of the intricate angle-dependent dynamics of a photoemission process in helium, spectrally and anisotropically structured by two-photon transitions through intermediate bound states. Using spectrally and angularly resolved attosecond electron interferometry, we characterize the complex-valued transition probability amplitude toward the photoelectron quantum state.

Specific chemical bond relaxation unraveled by analysis of shake-up satellites in the oxygen single site double core hole spectrum of CO.

We recently developed [A. Ferté, , , 2020, , 4359] a method to compute single site double core hole (ssDCH or K) spectra. We refer to that method as NOTA+CIPSI.

Advanced Computation Method for Double Core Hole Spectra: Insight into the Nature of Intense Shake-up Satellites.

Double core hole spectroscopy is an ideal framework for investigating photoionization shake-up satellites. Their important intensity in a single site double core hole (ssDCH) spectrum allows the exploration of the subtle mix of relaxation and correlation effects associated with the inherent multielectronic character of the shake-up process. We present a high-accuracy computation method for single photon double core-shell photoelectron spectra that combines a selected configuration interaction procedure with the use of non-orthogonal molecular orbitals to obtain unbiased binding energy and intensity.

Optimal Basis Set for Electron Dynamics in Strong Laser Fields: The case of Molecular Ion H.

A clear understanding of the mechanisms that control the electron dynamics in a strong laser field is still a challenge that requires interpretation by advanced theory. Development of accurate theoretical and computational methods, able to provide a precise treatment of the fundamental processes generated in the strong field regime, is therefore crucial. A central aspect is the choice of the basis for the wave function expansion.

Laser-induced blurring of molecular structure information in high harmonic spectroscopy.

High harmonic spectroscopy gives access to molecular structure with Angström resolution. Such information is encoded in the destructive interferences occurring between the harmonic emissions from the different parts of the molecule. By solving the time-dependent Schrödinger equation, either numerically or with the molecular strong-field approximation, we show that the electron dynamics in the emission process generally results in a strong spectral smoothing of the interferences, blurring the structural information.

Attosecond-resolved photoionization of chiral molecules.

Chiral light-matter interactions have been investigated for two centuries, leading to the discovery of many chiroptical processes used for discrimination of enantiomers. Whereas most chiroptical effects result from a response of bound electrons, photoionization can produce much stronger chiral signals that manifest as asymmetries in the angular distribution of the photoelectrons along the light-propagation axis. We implemented self-referenced attosecond photoelectron interferometry to measure the temporal profile of the forward and backward electron wave packets emitted upon photoionization of camphor by circularly polarized laser pulses.

Attosecond dynamics through a Fano resonance: Monitoring the birth of a photoelectron.

The dynamics of quantum systems are encoded in the amplitude and phase of wave packets. However, the rapidity of electron dynamics on the attosecond scale has precluded the complete characterization of electron wave packets in the time domain. Using spectrally resolved electron interferometry, we were able to measure the amplitude and phase of a photoelectron wave packet created through a Fano autoionizing resonance in helium.

Synthesis and characterization of attosecond light vortices in the extreme ultraviolet.

Infrared and visible light beams carrying orbital angular momentum (OAM) are currently thoroughly studied for their extremely broad applicative prospects, among which are quantum information, micromachining and diagnostic tools. Here we extend these prospects, presenting a comprehensive study for the synthesis and full characterization of optical vortices carrying OAM in the extreme ultraviolet (XUV) domain. We confirm the upconversion rules of a femtosecond infrared helically phased beam into its high-order harmonics, showing that each harmonic order carries the total number of OAM units absorbed in the process up to very high orders (57).

Self-Probing Spectroscopy of the SF6 Molecule: A Study of the Spectral Amplitude and Phase of the High Harmonic Emission.

We present characterizations of the attosecond pulse train produced in the high harmonic generation (HHG) from SF6 molecules irradiated by a strong pulsed laser field at 800 nm. At harmonic order 17, we observe a minimum in the amplitude of the emitted spectrum and a corresponding distortion in the phase. Our experimental results are compared to two models: a multicenter interference model focused on the effect of the structure of the SF6 molecule in HHG and a model focused on the interferences between multiple ionization channels in HHG.

Momentum transfer to a free floating double slit: realization of a thought experiment from the Einstein-Bohr debates.

We simultaneously measured the momentum transferred to a free-floating molecular double slit and the momentum change of the atom scattering from it. Our experimental results are compared to quantum mechanical and semiclassical models. The results reveal that a classical description of the slits, which was used by Einstein in his debate with Bohr, provides a surprisingly good description of the experimental results, even for a microscopic system, if momentum transfer is not ascribed to a specific pathway but shared coherently and simultaneously between both.

Theoretical study of Raman chirped adiabatic passage by X-ray absorption spectroscopy: highly excited electronic states and rotational effects.

Raman Chirped Adiabatic Passage (RCAP) is an efficient method to climb the vibrational ladder of molecules. It was shown on the example of fixed-in-space HCl molecule that selective vibrational excitation can thus be achieved by RCAP and that population transfer can be followed by X-ray Photoelectron spectroscopy [S. Engin, N.

Direct observation of spin-forbidden transitions through the use of suitably polarized light.

The study of excited triplet states of a molecular system is a difficult task because accessing them involves forbidden transitions from the singlet ground state. Nevertheless, absorption spectra of many molecules present, at low energies, the weak fingerprint of these triplet states. At higher energies this information is usually masked by the intense signal of the singlet states.

Excited state dynamics in SO2. III. An ab initio quantum study of single- and multi-photon ionization.

We present an ab initio quantum study of the photoelectron spectra of sulfur dioxide, based on wavepacket propagations on manifolds of ionic, and excited/Rydberg states. We obtain excellent agreement for two different cases. First, the one photon ionization case where we can reproduce all details of the experimental spectrum and demonstrate the influence of the conical intersection between two of the ionic states.

Communication: Theoretical prediction of the importance of the (3)B2 state in the dynamics of sulfur dioxide.

Even though the sulfur dioxide molecule has been extensively studied over the last decades, its photo-excitation dynamics is still unclear, due to its complexity, combining conical intersections, and spin-orbit coupling between a manifold of states. We present a comprehensive ab initio study of the intersystem crossing of the molecule in the low energy domain, based on a wave-packet propagation on the manifold of the lowest singlet and triplet states. Furthermore, spin-orbit couplings are evaluated on a geometry-dependent grid, and diabatized along with the different conical intersections.

Raman chirped adiabatic passage probed by X-ray spectroscopy.

We report a theoretical study of the selective vibrational excitation of a HCl molecule achieved by Raman chirped adiabatic passage (RCAP) and probed by X-ray photoelectron spectroscopy (XPS). It is demonstrated that HCl can be prepared in any vibrational level up to ν = 9 with nearly complete population inversion. We explore the effects of both the rotation of the molecule and of the temperature on the RCAP process, which is proved to be very robust.

Ab initio quantum study of the photodynamics and absorption spectrum for the coupled 1(1)A2 and 1(1)B1 states of SO2.

The nonadiabatic photoinduced dynamics occurring in the coupled 1(1)A(2) and 1(1)B(1) excited states of SO(2) is investigated using ab initio quantum dynamical methods. To this end, large scale calculations of the potential energy surfaces have been carried out at the multireference configuration interaction level. All vibrational degrees of freedom of the molecule are considered in the potential energy surface calculations and the quantum dynamical treatment.

Imaging orbitals with attosecond and Ångström resolutions: toward attochemistry?

The recently developed attosecond light sources make the investigation of ultrafast processes in matter possible with unprecedented time resolution. It has been proposed that the very mechanism underlying the attosecond emission allows the imaging of valence orbitals with Ångström space resolution. This controversial idea together with the possibility of combining attosecond and Ångström resolutions in the same measurements has become a hot topic in strong-field science.

Probing single-photon ionization on the attosecond time scale.

We study photoionization of argon atoms excited by attosecond pulses using an interferometric measurement technique. We measure the difference in time delays between electrons emitted from the 3s(2) and from the 3p(6) shell, at different excitation energies ranging from 32 to 42 eV. The determination of photoemission time delays requires taking into account the measurement process, involving the interaction with a probing infrared field.

Attosecond resolved electron release in two-color near-threshold photoionization of N2.

We have simulated two-color photoionization of N(2) by solving the time-dependent Schrödinger equation with a simple model accounting for the correlated vibronic dynamics of the molecule and of the ion N(2)(+). Our results, in very good agreement with recent experiments [Haessler et al., Phys.