Attosecond Transient Absorption Spectroscopy Research Articles

Initial electron thermalization in metals measured by attosecond transient absorption spectroscopy

Initial electron thermalization in metals measured by attosecond transient absorption spectroscopy

Attosecond Probing of Coherent Vibrational Dynamics in CBr4.

A coherent vibrational wavepacket is launched and manipulated in the symmetric stretch (a1) mode of CBr4, by impulsive stimulated Raman scattering (ISRS) from nonresonant 400 nm laser pump pulses with various peak intensities on the order of tens of 1012 W/cm2. Extreme ultraviolet (XUV) attosecond transient absorption spectroscopy (ATAS) records the wavepacket dynamics as temporal oscillations in XUV absorption energy at the bromine M4,5 3d3/2,5/2 edges around 70 eV. The results are augmented by nuclear time-dependent Schrödinger equation simulations. Slopes of the (Br 3d3/2,5/2)-110a1* core-excited state potential energy surface (PES) along the a1 mode are calculated to be -9.4 eV/Å from restricted open-shell Kohn-Sham calculations. Using analytical relations derived for the small-displacement limit and the calculated slopes of the core-excited state PES, a deeper insight into the vibrational dynamics is obtained by retrieving the experimental excursion amplitude of the vibrational wavepacket and the amount of population transferred to the vibrational first-excited state as a function of pump-pulse peak intensity. Experimentally, the results show that XUV ATAS is capable of resolving oscillations in the XUV absorption energy on the order of a few to tens of meV with tens of femtosecond time precision. This corresponds to change in C-Br bond length on the order of 10-4 to 10-3 Å. The results and the analytic relationships offer a clear physical picture, on multiple levels of understanding, of how the pump-pulse peak intensity controls the vibrational dynamics launched by nonresonant ISRS in the small-displacement limit.

Diagnostics of fs Laser‐Induced Plasmas in Solid Dielectrics

AbstractThe formation of dense plasmas inside dielectric materials by ultrashort laser pulses has many applications ranging from refractive‐index modifications to the formation of channels and voids. Furthermore, such plasmas enable the fundamental investigation of ultrafast non‐equilibrium dynamics in highly excited materials. The present paper provides an overview of current experimental approaches to investigating such plasmas. Much information about the plasma relaxation is obtained by measuring the spatial and temporal evolution of the dielectric properties of the excited material through time‐resolved absorption and phase‐shift measurements. In order to investigate and resolve the individual stages of plasma formation, experimental approaches with a temporal resolution beyond the capabilities of traditional optical pump‐probe studies are required. Recent examples for schemes that may enable the investigation of the plasma formation with sub‐cycle time resolution are thus reviewed. These include recent results from time‐resolved high‐harmonic generation as well as the two‐color pump‐probe analysis of non‐perturbative low‐order wave mixing for the tracking of strong‐field excitation dynamics. Alternative approaches employ attosecond transient absorption spectroscopy, attosecond polarization spectroscopy and nonlinear photoconductive sampling for resolving the temporal evolution of the carrier dynamics down to sub‐optical‐cycle timescales.

Controlling the bandwidth of high harmonic emission peaks with the spectral polarization of the driver.

We demonstrate a high harmonic-generation scheme that offers control over the bandwidth of the spectral peaks. The scheme uses a vectorial two-color driver with close central frequencies, generated by spectrally splitting a linearly polarized input femtosecond-duration laser pulse and subsequently recombining the two halves after their polarizations are made cross-elliptical and counter-rotating. This results in the generation of new emission channels that coalesce into broad odd-integer HHG peaks, the bandwidth of each being proportional to the frequency difference between the two colors, to the harmonic order and inversely proportional to the driver fields' ellipticities. Peak broadening to the extent that a supercontinuum is formed is also demonstrated. This source will find use in HHG applications benefiting from high-flux broadband extreme ultraviolet radiation, such as attosecond transient absorption spectroscopy.

Rotation in attosecond vibronic coherence spectroscopy for molecules

Excitation or ionization of a molecule by ultrafast laser pulses can create a superposition of electronic states, whose dynamics is influenced by the interplay of electronic coherence and nuclear motion, resulting in charge migration and possibly charge transfer. Probing the vibronic coherence is therefore vital to monitoring electronic dynamics and controlling chemical reactivity, as recently demonstrated in molecules via attosecond transient absorption spectroscopy (ATAS). However, theories supporting the interpretation of ATAS experiments neglect the effects of molecular rotation, often leading to inaccurate interpretation of experimental data. Here, we develop a comprehensive theory for ATAS of molecules encompassing the entire pump-probe process. Applying the theory to N2, we demonstrate that the emergence of coherent signals critically depends on the consideration of molecular rotation. This work contributes to close the gap between theory and ATAS experiments, paving the way for monitoring electronic motion and controlling chemical reactivity in diverse molecular systems.

Raman time-delay in attosecond transient absorption of strong-field created krypton vacancy

Strong field ionization injects a transient vacancy in the atom which is entangled to the outgoing photoelectron. When the electron is finally detached, the ion is populated at different excited states with part of coherence information lost. The preserved coherence of matter after interacting with intense short pulses has important consequences on the subsequent nonequilibrium evolution and energy relaxation. Here we employ attosecond transient absorption spectroscopy to measure the time-delay of resonant transitions of krypton vacancy during their creation. We have observed that the absorptions by the two spin-orbit split states are modulated at different paces when varying the time-delay between the near-infrared pumping pulse and the attosecond probing pulse. It is shown that the coupling of the ions with the remaining field leads to a suppression of ionic coherence. Comparison between theory and experiments uncovers that coherent Raman coupling induces time-delay between the resonant absorptions, which provides insight into laser-ion interactions enriching attosecond chronoscopy.

Attosecond-pump attosecond-probe x-ray spectroscopy of liquid water.

Attosecond-pump/attosecond-probe experiments have long been sought as the most straightforward method for observing electron dynamics in real time. Although there has been much success with overlapped near-infrared femtosecond and extreme ultraviolet attosecond pulses combined with theory, true attosecond-pump/attosecond-probe experiments have been limited. We used a synchronized attosecond x-ray pulse pair from an x-ray free-electron laser to study the electronic response to valence ionization in liquid water through all x-ray attosecond transient absorption spectroscopy (AX-ATAS). Our analysis showed that the AX-ATAS response is confined to the subfemtosecond timescale, eliminating any hydrogen atom motion and demonstrating experimentally that the 1b1 splitting in the x-ray emission spectrum is related to dynamics and is not evidence of two structural motifs in ambient liquid water.

Attosecond absorption and reflection spectroscopy of solids

Since their introduction, all-optical spectroscopy techniques based on attosecond radiation have gained the attention of the scientific community because of their energy and time resolution, combined with an easier experimental implementation with respect to other approaches based on charged particle detection. At the present time, almost ten years after the first application to a solid sample, attosecond transient absorption spectroscopy (ATAS) and attosecond transient reflection spectroscopy (ATRS) have established as powerful tools to investigate how electrons can be excited and accelerated in matter with short light pulses, a key requisite to establish ultrafast switches in quantum electronics and overcome the current rate of data processing and information encoding. In this work, we start with a historical overview of the first pioneering experiments to then introduce the fundamentals of both techniques. We conclude by discussing the current challenges and the possible future developments that are expected to bring ATAS and ATRS beyond their state of the art.

Few-femtosecond electronic and structural rearrangements of driven by the Jahn-Teller effect.

The Jahn-Teller effect (JTE) is central to the understanding of the physical and chemical properties of a broad variety of molecules and materials. Whereas the manifestations of the JTE in stationary properties of matter are relatively well studied, the study of JTE-induced dynamics is still in its infancy, largely owing to its ultrafast and non-adiabatic nature. For example, the time scales reported for the distortion of from the initial geometry to a nominal relaxed structure range from 1.85 fs over 10 ± 2 fs to 20 ± 7 fs. Here, by combining element-specific attosecond transient-absorption spectroscopy and quantum-dynamics simulations, we show that the initial electronic relaxation occurs within 5 fs and that the subsequent nuclear dynamics are dominated by the Q2 scissoring and Q1 symmetric stretching modes, which dephase in 41 ± 10 fs and 13 ± 3 fs, respectively. Significant structural relaxation is found to take place only along the e-symmetry Q2 mode. These results demonstrate that created by ionization of is best thought of as a highly fluxional species that possesses a long-time-averaged vibrational distribution centered around a structure. The methods demonstrated in our work provide guidelines for the understanding of Jahn-Teller driven non-adiabatic dynamics in other more complex systems.

Femtosecond symmetry breaking and coherent relaxation of methane cations via x-ray spectroscopy

Understanding the relaxation pathways of photoexcited molecules is essential to gain atomistic-level insight into photochemistry. We performed a time-resolved study of ultrafast molecular symmetry breaking through geometric relaxation (Jahn-Teller distortion) on the methane cation. Attosecond transient absorption spectroscopy with soft x-rays at the carbon K-edge revealed that the distortion occurred within 10 ± 2 femtoseconds after few-femtosecond strong-field ionization of methane. The distortion activated coherent oscillations in the asymmetric scissoring vibrational mode of the symmetry-broken cation, which were detected in the x-ray signal. These oscillations were damped within 58 ± 13 femtoseconds because vibrational coherence was lost with the energy redistributing into lower-frequency vibrational modes. This study completely reconstructs the molecular relaxation dynamics of this prototypical example and opens avenues for exploring complex systems.

Attosecond Monitoring of Nonadiabatic Molecular Dynamics by Transient X-ray Transmission Spectroscopy

Tracing the evolution of molecular coherences can provide a direct, unambiguous probe of nonadiabatic molecular processes, such as the passage through conical intersections of electronic states. Two techniques, attosecond transient absorption spectroscopy (ATAS) and Transient Redistribution of Ultrafast Electronic Coherences in Attosecond Raman Signals (TRUECARS), have been used or proposed for monitoring nonadiabatic molecular dynamics. Both techniques employ the transmission of a weak attosecond extreme-ultraviolet or X-ray probe to interrogate the molecule at controllable time delays with respect to an optical pump, thereby extracting dynamical information from transient spectral features. The connection between these techniques has not been firmly established yet. In this theoretical study, we provide a unified description of both transient transmission techniques, establishing their relationship as limits of the same pump-probe spectroscopy technique for different pulse parameter regimes. We demonstrate this by quantum dynamical simulations of thiophenol photodissociation and show how complementary coherence information can be revealed by the two techniques.

Ultrafast electron localization and screening in a transition metal dichalcogenide

The coupling of light to electrical charge carriers in semiconductors is the foundation of many technological applications. Attosecond transient absorption spectroscopy measures simultaneously how excited electrons and the vacancies they leave behind dynamically react to the applied optical fields. In compound semiconductors, these dynamics can be probed via any of their atomic constituents with core-level transitions into valence and conduction band. Typically, the atomic species forming the compound contribute comparably to the relevant electronic properties of the material. One therefore expects to observe similar dynamics, irrespective of the choice of atomic species via which it is probed. Here, we show in the two-dimensional transition metal dichalcogenide semiconductor MoSe2, that through a selenium-based core-level transition we observe charge carriers acting independently from each other, while when probed through molybdenum, the collective, many-body motion of the carriers dominates. Such unexpectedly contrasting behavior can be explained by a strong localization of electrons around molybdenum atoms following absorption of light, which modifies the local fields acting on the carriers. We show that similar behavior in elemental titanium metal [M. Volkov et al., Nat. Phys. 15, 1145-1149 (2019)]carries over to transition metal-containing compounds and is expected to play an essential role for a wide range of such materials. Knowledge of independent particle and collective response is essential for fully understanding these materials.

Apparatus for attosecond transient-absorption spectroscopy in the water-window soft-X-ray region

We present an apparatus for attosecond transient-absorption spectroscopy (ATAS) featuring soft-X-ray (SXR) supercontinua that extend beyond 450 eV. This instrument combines an attosecond table-top high-harmonic light source with mid-infrared (mid-IR) pulses, both driven by 1.7–1.9 mJ, sub-11 fs pulses centered at 1.76 upmum. A remarkably low timing jitter of sim 20 as is achieved through active stabilization of the pump and probe arms of the instrument. A temporal resolution of better than 400 as is demonstrated through ATAS measurements at the argon L_{2,3}-edges. A spectral resolving power of 1490 is demonstrated through simultaneous absorption measurements at the sulfur L_{2,3}- and carbon K-edges of OCS. Coupled with its high SXR photon flux, this instrument paves the way to attosecond time-resolved spectroscopy of organic molecules in the gas phase or in aqueous solutions, as well as thin films of advanced materials. Such measurements will advance the studies of complex systems to the electronic time scale.

Accurate Relativistic Real-Time Time-Dependent Density Functional Theory for Valence and Core Attosecond Transient Absorption Spectroscopy

First principles theoretical modeling of out-of-equilibrium processes observed in attosecond pump-probe transient absorption spectroscopy (TAS) triggering pure electron dynamics remains a challenging task, especially for heavy elements and/or core excitations containing fingerprints of scalar and spin-orbit relativistic effects. To address this, we formulate a methodology for simulating TAS within the relativistic real-time, time-dependent density functional theory (RT-TDDFT) framework, for both the valence and core energy regimes. Especially for TAS, full four-component (4c) RT simulations are feasible but computationally demanding. Therefore, in addition to the 4c approach, we also introduce the atomic mean-field exact two-component (amfX2C) Hamiltonian accounting for one- and two-electron picture-change corrections within RT-TDDFT. amfX2C preserves the accuracy of the parent 4c method at a fraction of its computational cost. Finally, we apply the methodology to study valence and near-L2,3-edge TAS processes of experimentally relevant systems and provide additional physical insights using relativistic nonequilibrium response theory.

Kramers–Kronig relation in attosecond transient absorption spectroscopy

The Kramers–Kronig relation (KKR) has a wide range of applications in extreme ultraviolet (XUV) and x-ray spectroscopy. However, the validity of KKR for many of these applications has not been systematically studied, while it is known to require careful attention in nonlinear and pump–probe experiments in optical domain spectroscopy. Here, we study the validity of KKR in XUV attosecond transient absorption spectroscopy pump–probe measurements both experimentally and theoretically using argon Fano resonances as a case study. Experiments are enabled by a phase-resolved method dubbed Complex Attosecond Transient-absorption Spectroscopy (CATS). Although the estimations based on the rotating-wave approximation suggest that KKR violation could be expected in the studied case, our results validate KKR and provide a solid basis for its application in a broad range of attosecond spectroscopy experiments.

Fishbone resonance structure in the attosecond transient absorption spectrum of graphene

We investigate the attosecond transient absorption spectroscopy (ATAS) of graphene by numerically solving four-band density-matrix equations, which demonstrates apparent fish bone resonance structures. To gain insight into these interesting structures, we exploit a simplified model that only considers the electrons of $\Gamma$ and M points in the Brillouin zone. With the help of this model, we can analytically express the ATAS spectrum as the sum of zeroth- and first-order Bessel functions in the variables of the strength and frequency of the infrared pump field as well as the effective mass of electrons at the $\Gamma$ and M points. Lorentzian and Fano line shapes in the absorption spectrum are addressed. The fish bone structure consists of periodic V-shaped structure that can be explained by first-order Bessel functions and its tilt angle is solely determined by the frequency of the pump laser. The periodicity of the V-shaped structure in the fish bone originates from the periodic dependence of the Lorentzian and Fano line shapes of the absorption spectrum on the time delay between the pump and probe lasers. Compared with the numerical results, our analytical theory can qualitatively or even quantitatively predict the zeroth- and first-order fringes in the fish bone structures of the ATAS spectrum. The gauge issues in the numerical simulations are also discussed.

Core-resonance line-shape analysis of atoms undergoing strong-field ionization

Using attosecond transient absorption spectroscopy for time delays where the near-infrared pump and the extreme ultraviolet (XUV) probe pulses overlap, sub-cycle structures in the build-up of absorption lines in xenon ions are investigated as a function of the pump intensity during strong-field ionization. We observe a half-cycle-periodic change in the line-shape asymmetry of the ionic 4d–5p resonances. Analyzing the line shapes, we find that in particular the phase of the induced dipole emission is modified, and the magnitude of this phase modulation decreases with increasing laser intensity. We discuss the influence of ground state depletion on interfering pathways involved in XUV-assisted strong-field ionization.

Decoherence and Revival in Attosecond Charge Migration Driven by Non-adiabatic Dynamics.

Attosecond charge migration is a periodic evolution of the charge density at specific sites of a molecule on a time scale defined by the energy intervals between the electronic states involved. Here, we report the observation of charge migration in neutral silane (SiH4) in 690 as, its decoherence within 15 fs, and its revival after 40-50 fs, using X-ray attosecond transient absorption spectroscopy. We observe the migration of charge as pairs of quantum beats with a characteristic spectral phase in the transient spectrum, in agreement with theory. The decay and revival of the degree of electronic coherence is found to be a result of both adiabatic and non-adiabatic dynamics in the populated Rydberg and valence states. The experimental results are supported by fully quantum-mechanical ab-initio calculations that include both electronic and nuclear dynamics, which additionally support the experimental evidence that conical intersections can mediate the transfer of electronic coherence from an initial superposition state to another one involving a different lower-lying state.

Pinpointing the macroscopic signatures of attosecond transient absorption in helium: Reshaped spectral splitting and persistent quantum beating

Although attosecond transient absorption spectroscopy (ATAS) has been widely used in the study of ultrafast dynamics of atoms, molecules, and solids, there is a need for further theoretical exploration of macroscopic effects beyond the response of single atoms. Here, the extreme ultraviolet (XUV) absorbance of He atoms in the presence of a delayed near-infrared (NIR) pulse is studied theoretically, from the limit of dilute-gas medium to high densities. By numerically solving the time-dependent Schr\"odinger equation coupled with Maxwell's equations, we elucidate the macroscopic signatures in the absorption spectrum of an optically dense medium, including previously recognized XUV spectral pulse shaping, a complex spectral splitting, and a persistent quantum beating, based on the energies of the states involved. An analytical expression for optical density is deduced directly to pinpoint the physical origins of the various absorption features in a quantitative way, which helps one grasp the intuitive picture of the macroscopic absorption spectrum and provides guidance to explore applications such as optical pulse shaping and XUV molecular quantum beat spectroscopy.

Multipolariton control in attosecond transient absorption of autoionizing states

Tunable attosecond transient absorption spectroscopy is an ideal tool for studying and manipulating autoionization dynamics in the continuum. We investigate near-resonant two-photon couplings between the bright 3s^-1 4p and dark 3s^-1 4f autoionizing states of argon that lead to Autler-Townes like interactions, forming entangled light-matter states, or polaritons. We observe that one-photon couplings with intermediate dark states play an important role in this interaction, leading to the formation of multiple polaritonic branches whose energies exhibit avoided crossings as a function of the dressing-laser frequency. Our experimental measurements and theoretical essential-state simulations show good agreement and reveal how the delay, frequency, and intensity of the dressing pulse govern the properties of autoionizing polariton multiplets. These results demonstrate new pathways for quantum control of autoionizing states with optical fields.