Attosecond electron-spin dynamics in Xe 4d photoionization
Shiyang Zhong, Jimmy Vinbladh, David Busto, Richard J. Squibb, Marcus Isinger, Lana Neoričić, Hugo Laurell, Robin Weissenbilder, Cord L. Arnold, Raimund Feifel,… 展开作者
Shiyang Zhong, Jimmy Vinbladh, David Busto, Richard J. Squibb, Marcus Isinger, Lana Neoričić, Hugo Laurell, Robin Weissenbilder, Cord L. Arnold, Raimund Feifel, Jan Marcus Dahlström, Göran Wendin, Mathieu Gisselbrecht, Eva Lindroth, Anne L'Huillier
The photoionization of xenon atoms in the 70-100 eV range reveals several fascinating physical phenomena such as a giant resonance induced by the dynamic rearrangement of the electron cloud after photon absorption, an anomalous branching ratio between intermediate Xe$^+$ states separated by the spin-orbit interaction and multiple Auger decay processes. These phenomena have been studied in the past, using in particular synchrotron radiation, but without access to real-time dynamics. Here, we study the dynamics of Xe 4d photoionization on its natural time scale combining attosecond interferometry and coincidence spectroscopy. A time-frequency analysis of the involved transitions allows us to identify two interfering ionization mechanisms: the broad giant dipole resonance with a fast decay time less than 50 as and a narrow resonance at threshold induced by spin-flip transitions, with much longer decay times of several hundred as. Our results provide new insight into the complex electron-spin dynamics of photo-induced phenomena.
We determine and analyze the quantum phases and time delays in photoionization and photorecombination of valence 3p and 3s electrons of argon using the Kohn-Sham local density functional approach. The time-dependent local density approximation (TDLDA) is used to account for the electron correlation. Resulting attosecond Wigner-Smith time delays show excellent agreements with two recent independent experiments on argon that measured the relative 3s-3p time delay in photoionization [Physical Review Letters {\bf 106}, 143002 (2011)] and the delay in 3p photorecombination [Physical Review Letters …
In a seminal article, Fano predicts that absorption of light occurs preferably with increase of angular momentum. Here we generalize Fano's propensity rule to laser-assisted photoionization, consisting of absorption of an extreme-ultraviolet photon followed by absorption or emission of an infrared photon. The predicted asymmetry between absorption and emission leads to incomplete quantum interference in attosecond photoelectron interferometry. It explains both the angular-dependence of the photoionization time delays and the delay-dependence of the photoelectron angular distributions. Our theo…
Attosecond photoionization delays have mostly been interpreted within the single-particle approximation of multi-electron systems. The strong electron correlation between the photoionization channels associated with the 3p and 3s orbitals of argon presents an interesting arena where this single-particle approximation breaks down. Around photon energies of 42~eV, the 3s photoionization channel of argon experiences a ``Cooper-like" minimum, which is exclusively the result of inter-electronic correlations with the 3p shell. Photoionization delays around this ``Cooper-like" minimum have been predi…
We investigate ionization of neon atoms by an isolated attosecond pump pulse in the presence of two coherent extreme ultraviolet or x-ray probe fields. The probe fields are tuned to a core-valence transition in the residual ion and induce spectral shearing of the photoelectron distributions. We show that the photoelectron-ion coincidence signal contains an interference pattern that depends on the temporal structure of the attosecond pump pulse and the stimulated core-valence transition. Many-body perturbation theory is used to compute "atomic response times" for the processes and we find strik…
The initial insight into time delay in Mn photoionization in the region of the $3p \to 3d$ giant autoionization resonance is gained in the framework of the "spin-polarized" random phase approximation with exchange. The dramatic effect of the giant autoionization resonance on time delay of photoemission from the $3d$ and $4s$ valence subshells of the Mn atom is unraveled. Strong sensitivity of the time delay of the $4s$ photoemission to the final-state term of the ion-remainder [${\rm Mn^{+}}(4s^{1},$$^{5}S)$ vs.~${\rm Mn^{+}}(4s^{1},$$^{7}S)$] is discovered. It is shown that photoionization ti…
We present a theory of time-resolved photoionisation in the presence of a vortex beam. In a pump-probe setup, an extreme ultraviolet or an x-ray pump pulse triggers ionization, which is probed by a synchronized infrared pulse with non-zero orbital angular momentum. We show, how this property of the probe pulse affects the electron dynamics upon ionization, in a way that is independent of the initial and final angular momentum states of the ionizing system.
The effects of confinement resonances on photoelectron group delay (Wigner time delay) following ionization of an atom encapsulated inside a C$_{60}$ cage have been studied theoretically using both relativistic and non-relativistic random phase approximations. The results indicate clearly the resonant character of the confinement oscillations in time delay of the $4d$ shell of Xe@C$_{60}$ and present a most direct manifestation of Wigner time delay. These oscillations were missed in a previous theoretical investigation of Ar@C$_{60}$ [PRL 111, 203003 (2013)]
We photoionize nitrogen molecules with a train of extreme ultraviolet attosecond pulses together with a weak infrared field. We measure the phase of the two-color two-photon ionization transition (molecular phase) for different states of the ion. We observe a 0.76 $π$ shift for the electrons produced in the ionization channels leading to the X$^2 Σ_g^+$, $v'=1$ and $v'=2$ states. We relate this phase shift to the presence of a complex resonance in the continuum. By providing both a high spectral and temporal resolution, this general approach gives access to the evolution of extremely short liv…
We study the role of electron-electron correlation in the ground-state of Ne, as well as in photoionization dynamics induced by an attosecond XUV pulse. For a selection of central photon energies around 100 eV, we find that while the mean-field time-dependent Hartree-Fock method provides qualitatively correct results for the total ionization yield, the photoionization cross section, the photoelectron momentum distribution as well as for the time-delay in photoionization, electron-electron correlation is important for a quantitative description of these quantities.
We investigate the photoionization spectrum of helium by attosecond XUV pulses both in the spectral region of doubly excited resonances as well as above the double ionization threshold. In order to probe for convergence, we compare three techniques to extract photoelectron spectra from the wavepacket resulting from the integration of the time-dependent Schroedinger equation in a finite-element discrete variable representation basis. These techniques are: projection on products of hydrogenic bound and continuum states, projection onto multi-channel scattering states computed in a B-spline clos…
We revisit the time-resolved photoemission in neon atoms as probed by attosecond streaking. We calculate streaking time shifts for the emission of 2p and 2s electrons and compare the relative delay as measured in a recent experiment by Schultze et al. [Science 328, 1658 (2010)]. The B-spline R-matrix method is employed to calculate accurate Eisenbud-Wigner-Smith time delays from multi- electron dipole transition matrix elements for photoionization. The additional laser field-induced time shifts in the exit channel are obtained from separate, time-dependent simulations of a full streaking proce…
A technique for measuring photoionization time delays with attosecond precision is combined with calculations of photoionization matrix elements to demonstrate how multi-electron dynamics affect photoionization time delays in carbon dioxide. Electron correlation is observed to affect the time delays through two mechanisms: autoionization of molecular Rydberg states and accelerated escape from a continuum shape resonance.
Using a spectrally resolved electron interferometry technique, we measure photoionization time delays between the $3s$ and $3p$ subshells of argon over a large 34-eV energy range covering the Cooper minima in both subshells. The observed strong variations of the $3s-3p$ delay difference, including a sign change, are well reproduced by theoretical calculations using the Two-Photon Two-Color Random Phase Approximation with Exchange. Strong shake-up channels lead to photoelectrons spectrally overlapping with those emitted from the $3s$ subshell. These channels need to be included in our analysis …
We study laser-assisted photoionization by attosecond pulses using a time-independent formalism based on diagrammatic many-body perturbation theory. Our aim is to provide an ab inito route to the "delays" for this above-threshold ionization process, which is essential for a quantitative understanding of attosecond metrology. We present correction curves for characterization schemes of attosecond pulses, such as "streaking", that account for the delayed atomic response in ionization from neon and argon. We also verify that photoelectron delays from many-electron atoms can be measured using simi…
We report measurements of energy-dependent attosecond photoionization delays between the two outer-most valence shells of N$_2$O and H$_2$O. The combination of single-shot signal referencing with the use of different metal foils to filter the attosecond pulse train enables us to extract delays from congested spectra. Remarkably large delays up to 160 as are observed in N$_2$O, whereas the delays in H$_2$O are all smaller than 50 as in the photon-energy range of 20-40 eV. These results are interpreted by developing a theory of molecular photoionization delays. The long delays measured in N$_2$O…
Using extreme-ultraviolet attosecond-pulse-trains, we investigate the photoionization dynamics of a Helium atom in the presence of moderately-strong (~10^12 W/cm^2) femtosecond laser pulses. The electronic structure of a laser-dressed atom is traced in real-time through precision measurements of ion-yields and photo-electron angular distributions. Quantum interferences between photo-excitation paths are interpreted using the Floquet formalism. As the laser pulse intensity ramps on femtosecond timescales, we observe transitions between ionization channels mediated by different atomic resonances…
A Kohn-Sham time-dependent local-density-functional scheme is utilized to predict attosecond time delays of xenon 4d photoionization that involves the 4d giant dipole resonance and Cooper minimum. The fundamental effect of electron correlations to uniquely determine the delay at both regions is demonstrated. In particular, for the giant dipole resonance, the delay underpins strong collective effect, emulating the recent prediction at C60 giant plasmon resonance [T. Barillot et al, Phys. Rev. A 91, 033413 (2015)]. For the Cooper minimum, a qualitative similarity with a photorecombination experi…
We study photoionization of various noble gas atoms by attosecond pulses produced in High Harmonic Generation (HHG). We use a pump-probe experiment to measure the time delays of electrons photoionized from Neon, Argon, and Krypton relative to those photoionized from Helium atoms. The Attosecond Pulse Train (APT) is characterized and the relative delay in photoionization of various noble gases is measured. The photoionization delay of Ne, Ar, and Kr is determined using previously calculated values for the He atomic delay and the delay associated with the probe process.
We study experimentally the influence of the intensity of the infrared (IR) probe field on attosecond pulse train (APT) phase measurements performed with the RABITT method (Reconstruction of Attosecond Beating by Interference in Two-Photon Transitions). We find that if a strong IR field is applied, the attosecond pulses will appear to have lower-than-actual chirp rates. We also observe the onset of the streaking regime in the breakdown of the weak-field RABITT conditions. We perform a Fourier-analysis of harmonic and sideband continuum states and show that the mutual phase relation of the harm…
We use the soft photon approximation to extract the Wigner time delay from atomic two-color photoionization experiments. Unlike the strong field approximation, the present method does not require introduction of the Coulomb-laser coupling corrections and enables one to extract the Wigner time delay directly from attosecond time delay measurements.
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. Here we implement a self-referenced attosecond photoelectron interferometry to measure the temporal profile of the forward and backward electron wavepackets emitted upon photoionizatio…
We present the first numerical simulation of the time delay in the photoionization of the simplest diatomic molecule H$_2^+$ as observed by attosecond streaking. We show that the strong variation of the Eisenbud-Wigner-Smith time delay as a function of energy and emission angle becomes observable in the streaking time shift provided laser field-induced components are accounted for. The strongly enhanced photoemission time shifts are traced to destructive Cohen-Fano (or two-center) interferences. Signatures of these interferences in the streaking trace are shown to be enhanced when the ionic fr…
The creation of superpositions of hole states via single-photon ionization using attosecond extreme-ultraviolet pulses is studied with the time-dependent configuration interaction singles (TDCIS) method. Specifically, the degree of coherence between hole states in atomic xenon is investigated. We find that interchannel coupling not only affects the hole populations, it also enhances the entanglement between the photoelectron and the remaining ion, thereby reducing the coherence within the ion. As a consequence, even if the spectral bandwidth of the ionizing pulse exceeds the energy splittings …
We study the temporal aspects of laser-assisted extreme ultraviolet (XUV) photoionization using attosecond pulses of harmonic radiation. The aim of this paper is to establish the general form of the phase of the relevant transition amplitudes and to make the connection with the time-delays that have been recently measured in experiments. We find that the overall phase contains two distinct types of contributions: one is expressed in terms of the phase-shifts of the photoelectron continuum wavefunction while the other is linked to continuum--continuum transitions induced by the infrared (IR) la…
The photoionization of the CO molecule from the C$-1s$ orbital does not obey the Franck-Condon approximation, as a consequence of the nuclear recoil that accompanies the direct emission and intra-molecular scattering of the photoelectron. We use an analytical model to investigate the temporal signature of the entangled nuclear and electronic motion in this process. We show that the photoelectron emission delay can be decomposed into its localization and resonant-confinement components. Finally, photoionization by a broadband soft-x-ray pulse results in a coherent vibrational ionic state with a…
This tutorial presents an introduction to the interaction of light and matter on the attosecond timescale. Our aim is to detail the theoretical description of ultra-short time-delays, and to relate these to the phase of extreme ultraviolet (XUV) light pulses and to the asymptotic phase-shifts of photoelectron wave packets. Special emphasis is laid on time-delay experiments, where attosecond XUV pulses are used to photoionize target atoms at well-defined times, followed by a probing process in real time by a phase-locked, infrared laser field. In this way, the laser field serves as a "clock" to…
We present a new theoretical approach to attosecond laser-assisted photo- and Compton ionization. Attosecond x-ray absorption and scattering are described by $\hat{\mathrsfs{S}}^{(1,2)}$-matrices, which are coherent superpositions of "monochromatic" $\hat{S}^{(1,2)}$-matrices in a laser-modified Furry representation. Besides refining the existing theory of the soft x-ray photoelectron attosecond streak camera and spectral phase interferometry (ASC and ASPI), we formulate a theory of hard x-ray photoelectron and Compton ASC and ASPI. The resulting scheme has a simple structure and leads to clos…
We present the experimental observation of two-center interference in the ionization time delays of Kr2. Using attosecond electron-ion-coincidence spectroscopy, we simultaneously measure the photoionization delays of krypton monomer and dimer. The relative time delay is found to oscillate as a function of the electron kinetic energy, an effect that is traced back to constructive and destructive interference of the photoelectron wave packets that are emitted or scattered from the two atomic centers. Our interpretation of the experimental results is supported by solving the time-independent Schr…
We describe numerically the ionization process induced by linearly and circularly polarized XUV attosecond laser pulses on an aligned atomic target, specifically, the excited state Ne$^*(1s^22s^22p^5[{}^2\text{P}^\text{o}_{1/2}]3s[^1\text{P}^o])$. We compute the excited atomic state by applying the time-dependent restricted-active-space self-consistent field (TD-RASSCF) method to fully account for the electronic correlation. We find that correlation-assisted ionization channels can dominate over channels accessible without correlation. We also observe that the rotation of the photoelectron mom…
We describe in detail how attosecond delays in laser-assisted photoionization can be computed using perturbation theory based on two-photon matrix elements. Special emphasis is laid on above-threshold ionization, where the electron interacts with an infrared field after photoionization by an extreme ultraviolet field. Correlation effects are introduced using diagrammatic many-body theory to the level of the random-phase approximation with exchange (RPAE). Our aim is to provide an ab initio route to correlated multi-photon processes that are required for an accurate description of experiments o…
We study the photoionization of argon atoms close to the 3s$^2$3p$^6$ $\rightarrow$ 3s$^1$3p$^6$4p $\leftrightarrow$ 3s$^2$3p$^5$ $\varepsilon \ell$, $\ell$=s,d Fano window resonance. An interferometric technique using an attosecond pulse train, i.e. a frequency comb in the extreme ultraviolet range, and a weak infrared probe field allows us to study both amplitude and phase of the photoionization probability amplitude as a function of photon energy. A theoretical calculation of the ionization process accounting for several continuum channels and bandwidth effects reproduces well the experimen…
Extracting single photoionization time delays associated with atomic (or molecular) species from attosecond time scale two-photon experiments usually relies on the theoretical description of continuum-continuum transitions. The available models for those processes predict a universal phase contribution, independent of the angular quantum numbers of final states. However, a recent experimental-theoretical study [Fuchs, \emph{et al.} Optica 7, 154 (2020)] determined a sizable time delay dependence on the angular momentum of near-threshold photoelectrons. In this study, we present an analytical m…
Characterizing time delays in molecular photoionization as a function of the ejected electron emission direction relative to the orientation of the molecule and the light polarization axis pro-vides unprecedented insights into the attosecond dynamics induced by extreme ultraviolet or X-ray one-photon absorption, including the role of electronic correlation and continuum resonant states. Here, we report completely resolved experimental and computational angular depend-ence of single-photon ionization delays in NO molecules across a shape resonance, relying on synchrotron radiation and time inde…
We theoretically study time-resolved photoemission in atoms as probed by attosecond streaking. We review recent advances in the study of the photoelectric effect in the time domain and show that the experimentally accessible time shifts can be decomposed into distinct contributions that stem from the field-free photoionization process itself and from probe-field induced corrections. We perform accurate quantum-mechanical as well as classical simulations of attosecond streaking for effective one-electron systems and determine all relevant contributions to the time delay with attosecond precisio…
Quantum mechanically, photoionization can be fully described by the complex photoionization amplitudes that describe the transition between the ground state and the continuum state. Knowledge of the value of the phase of these amplitudes has been a central interest in photoionization studies and newly developing attosecond science, since the phase can reveal important information about phenomena such as electron correlation. We present a new attosecond-precision interferometric method of angle-resolved measurement for the phase of the photoionization amplitudes, using two phase-locked Extreme …
We develop a novel technique for modeling of atomic and molecular ionization in superposition of XUV and IR fields with characteristics typical for attosecond streaking and RABBITT experiments. The method is based on solving the time-dependent Schrödinger equation in the coordinate frame expanding along with the photoelectron wave packet. The efficiency of the method is demonstrated by calculating angular anisotropy of photoemission time delay of the H$_2^+$ ion in a field configuration of recent RABBITT experiments.
Measured photoionization time delays may exhibit large variations as a function of the emission angles, even for spherically symmetric targets, as shown in recent RABBITT (reconstruction of attosecond beating by interference of two-photon transitions) experiments. The contributions from different pathways to the two-photon quantum channels can already explain the observed phase jumps that shape those angular distributions. Here, we propose a simple analytical model to describe angularly-resolved RABBITT spectra as a function of the relative polarization angle between the ionizing attosecond pu…
We analyze the time delay between emission of photoelectrons from the outer valence $ns$ and $np$ sub-shells in noble gas atoms following absorption of an attosecond XUV pulse. By solving the time dependent Schrödinger equation and carefully examining the time evolution of the photoelectron wave packet, we establish the apparent "time zero" when the photoelectron leaves the atom. Various processes such as elastic scattering of the photoelectron on the parent ion and many-electron correlation affect the quantum phase of the dipole transition matrix element, the energy dependence of which define…
We develop a first-principles simulation method for attosecond time-resolved photoelectron spectroscopy. This method enables us to directly simulate the whole experimental processes, including excitation, emission and detection on equal footing. To examine the performance of the method, we use it to compute the reconstruction of attosecond beating by interference of two-photon transitions (RABBITT) experiments of gas-phase Argon. The computed RABBITT photoionization delay is in very good agreement with recent experimental results from [Klünder et al, Phys. Rev. Lett. 106 143002 (2011)] and [Gu…
Photoionization from energetically distinct electronic states may have a relative time delay of tens of attoseconds. Here we demonstrate that pulses of optical vortices allow measuring such attoseconds delays from magnetic sublevels, even from a spherically symmetric target. The difference in the time delay is substantial and exhibits a strong angular dependence. Furthermore, we find an atomic scale variation in the time delays depending on the target orbital position in the laser spot. The findings offer thus a qualitatively new way for a spatio-temporal sensing of the magnetic states from wh…
We investigate the angle-resolved photoelectron spectra from laser-assisted photoionization for helium and neon atoms using an \textit{ab initio} method based on time-dependent surface flux and configuration interaction singles. We find that the shape of the distributions can be interpreted using a propensity rule, an intrinsic difference in the absorption and emission processes, as well as interference effects between multiple paths to the final angular momentum state. In neon we find that the difference between absorption and emission is hidden in the first sideband due to the multiple compe…
Light-induced states are commonly observed in the photoionization spectra of laser-dressed atoms. The properties of autoionizing polaritons, entangled states of light and Auger resonances, however, are largely unexplored. We employ attosecond transient-absorption spectroscopy to study the evolution of autoionizing states in argon, dressed by a tunable femtosecond laser pulse. The avoided crossings between the $3s^{-1}4p$ and several light-induced states indicates the formation of polariton multiplets. We measure a controllable stabilization of the polaritons against ionization, in excellent ag…
Attosecond interferometry (AI) is an experimental technique based on ionizing a system with an attosecond pulse train in the presence of an assisting laser. This assisting laser provides multiple pathways for the photoelectron wave packet to reach the same final state, and interference of these pathways can be used to probe properties of matter. The mechanism of AI is well-understood for isolated atoms and molecules in the gas phase, but not so much in the condensed phase, especially if the substrate under study is transparent. Then, additional pathways open up for the electron due to scatteri…
Quantum coherence plays a fundamental role in the study and control of ultrafast dynamics in matter. In the case of photoionization, entanglement of the photoelectron with the ion is a well known source of decoherence when only one of the particles is measured. Here we investigate decoherence due to entanglement of the radial and angular degrees of freedom of the photoelectron. We study two-photon ionization via the 2s2p autoionizing state in He using high spectral resolution photoelectron interferometry. Combining experiment and theory, we show that the strong dipole coupling of the 2s2p and …
Time-dependent Hole States in Multiconfigurational Time-Dependent Hartree-Fock Approaches: Applications in Photoionization of Water Molecule
Shanghai Jiao Tong University（上海交通大学）；RIKEN Center for Interdisciplinary Theoretical and Mathematical Sciences (iTHEMS)（理化学研究所交叉理论数学科学中心（iTHEMS））；RIKEN Center for Computational Science (R-CCS)（理化学研究所计算科学中心（R-CCS））；The University of Tokyo（东京大学）
We explore the escape geometry of four electrons a few eV above threshold following single-photon absorption from the ground state of Be. We find that the four electrons leave the atom on the vertices of a pyramid instead of a previously-predicted tetrahedron. To illustrate the physical mechanisms of quadruple ionization we use a momentum transferring attosecond collision scheme which we show to be in accord with the pyramid break-up pattern.
