Attosecond Transient Absorption Spectroscopy Research Articles

Efficient table-top beamline for attosecond molecular and solid-state dynamics at the carbon K-edge

SynopsisA harmonic continuum extending up to 375 eV is generated from 750 μJ, 9 fs mid-IR pulses centered at 1300 nm. The development of this source and its use for attosecond transient absorption spectroscopy experiments at the carbon K-edge are discussed.

Attosecond transient-absorption spectroscopy in one-dimensional periodic crystals

We investigate theoretically the application of attosecond transient-absorption spectroscopy to a one-dimensional periodic crystal in a regime where the dynamical Franz-Keldysh effect is presented around the energy gap. It is found that in the presence of a few-cycle dressing pulse the delay-dependent absorption spectrogram from the numerically exactly solvable model exhibits a general feature of the V-shaped fringes of subcycle oscillations. This structure represents femtosecond-resolved transient modulation of the conductivity, which is similar to recent experimental observation. We identify a regime where the higher-order even oscillation frequency becomes remarkable in the absorption spectrum for using the midinfrared pump laser. An analytical formula is also developed with the two-band approximation in order to facilitate analysis of the absorption spectrum. Our result shows that the full information on the momentum-dependent band gap across the entire Brillouin zone is encoded into the absorption spectrogram, thus suggesting an all-optical method to reconstruct the one-dimensional gap structure. The reconstruction feasibility is successfully demonstrated by a two-step algorithm even if considering the effect of noise. Moreover, we derive an analytical expression of the delay- and frequency-dependent conductivity with some additional assumptions. Some important features are successfully interpreted in terms of this analytical approach.

Attosecond precision in delay measurements using transient absorption spectroscopy.

Accessing attosecond (as) dynamics directly in the time domain has been achieved by several pioneering experiments over the course of the last decade. Extreme ultraviolet (XUV) group delays and, later, ionization time delays on the order of a few attoseconds have been extracted by photoemission or high-harmonic spectroscopy. Here, we present and benchmark an approach based on attosecond transient absorption spectroscopy to quantify deliberately induced delays by employing resonant photoexcitation of three XUV transitions with a precision of less than 5 as. While here we quantify the sensitivity to these delays via a chirp on the attosecond pulse by using thin-foil metallic filters, the method enables future studies of attosecond delays probed through resonant excitations.

Disentangling conical intersection and coherent molecular dynamics in methyl bromide with attosecond transient absorption spectroscopy

Attosecond probing of core-level electronic transitions provides a sensitive tool for studying valence molecular dynamics with atomic, state, and charge specificity. In this report, we employ attosecond transient absorption spectroscopy to follow the valence dynamics of strong-field initiated processes in methyl bromide. By probing the 3d core-to-valence transition, we resolve the strong field excitation and ensuing fragmentation of the neutral σ* excited states of methyl bromide. The results provide a clear signature of the non-adiabatic passage of the excited state wavepacket through a conical intersection. We additionally observe competing, strong field initiated processes arising in both the ground state and ionized molecule corresponding to vibrational and spin-orbit motion, respectively. The demonstrated ability to resolve simultaneous dynamics with few-femtosecond resolution presents a clear path forward in the implementation of attosecond XUV spectroscopy as a general tool for probing competing and complex molecular phenomena with unmatched temporal resolution.

Direct mapping of curve-crossing dynamics in IBr by attosecond transient absorption spectroscopy.

The electronic character of photoexcited molecules can abruptly change at avoided crossings and conical intersections. Here, we report direct mapping of the coupled interplay between electrons and nuclei in a prototype molecule, iodine monobromide (IBr), by using attosecond transient absorption spectroscopy. A few-femtosecond visible pulse resonantly excites the [Formula: see text], Y(0+), and Z(0+) states of IBr, and the photodissociation dynamics are tracked with an attosecond extreme-ultraviolet pulse that simultaneously probes the I-4d and Br-3d core-level absorption edges. Direct comparison with quantum mechanical simulations unambiguously identifies the absorption features associated with adiabatic and diabatic channels at the B/Y avoided crossing and concurrent two-photon dissociation processes that involve the Y/Z avoided crossing. The results show clear evidence for rapid switching of valence-electronic character at the avoided crossing.

Analytical Theory of Attosecond Transient Absorption Spectroscopy of Perturbatively Dressed Systems

A theoretical description of attosecond transient absorption spectroscopy for temporally and spatially overlapping XUV and optical pulses is developed, explaining the signals one can obtain in such an experiment. To this end, we employ a two-stage approach based on perturbation theory, which allows us to give an analytical expression for the transient absorption signal. We focus on the situation in which the attosecond XUV pulse is used to create a coherent superposition of electronic states. As we explain, the resulting dynamics can be detected in the spectrum of the transmitted XUV pulse by manipulating the electronic wave packet using a carrier-envelope-phase-stabilized optical dressing pulse. In addition to coherent electron dynamics triggered by the attosecond pulse, the transmitted XUV spectrum encodes information on electronic states made accessible by the optical dressing pulse. We illustrate these concepts through calculations performed for a few-level model.

Multiple-fringe structure of attosecond transient absorption spectrum driven by mid-infrared laser

We theoretically investigate the delay-dependent attosecond transient absorption spectra in the helium atom dressed by an infrared laser pulse in the wavelength range of 800–2400 nm. By numerically solving the three-dimensional time-dependent Schrodinger equation, we find that the absorption spectrogram exhibits a multiple-fringe structure for using the mid-infrared dressing pulse. The quantitative calculation of the transition matrix between different Floquet states provides direct evidence on the origin of the multiple-fringe structure. Our result shows that the wavelength of the dressing pulse is an important parameter and the unique feature of attosecond transient absorption spectroscopy can be induced in the mid-infrared regime.

State-Resolved Probing of Attosecond Timescale Molecular Dipoles.

We report an experimental study of iodomethane attosecond transient absorption spectroscopy (ATAS) in the region of iodine 4d core-to-valence/Rydberg excitation. Similar to previous atomic experiments, extreme ultraviolet near-infrared (XUV-NIR) delay-dependent absorbance changes reflect a light-induced phase due to an NIR-field driven AC Stark shift of the excited states, as well as pathway interferences arising from couplings between neighboring states. As a novel aspect of molecular ATAS, we observe pronounced differences between the ATAS signatures of valence and Rydberg states. While the core-to-valence transitions carry the majority of the XUV oscillator strength, the core-to-Rydberg transitions are dominantly affected by a moderately strong, nonionizing NIR field. Our experimental findings are corroborated by ab initio calculations and ATAS simulations.

Attosecond transient-absorption spectroscopy of polar molecules

We apply attosecond transient absorption spectroscopy (ATAS) to explore the effects of a nonzero permanent dipole on electron dynamics at the subfemtosecond scale, exemplified in the polar LiF molecule. In contrast with nonpolar systems, a familiar feature of the ATA spectra--the light-induced structures--are observed adjacent to a bright state. Moreover, a previously unobserved ladder structure is identified. The new observations are analyzed in the context of a model based on fixed-nuclei adiabatic states, supported by full numerical simulations. Analytic calculations originating in the adiabatic model shed light on the nature and origins of the new findings.

Ab Initio Simulation of Attosecond Transient Absorption Spectroscopy in Two-Dimensional Materials

We extend the first-principles analysis of attosecond transient absorption spectroscopy to two-dimensional materials. As an example of two-dimensional materials, we apply the analysis to monolayer hexagonal boron nitride (h-BN) and compute its transient optical properties under intense few-cycle infrared laser pulses. Nonadiabatic features are observed in the computed transient absorption spectra. To elucidate the microscopic origin of these features, we analyze the electronic structure of h-BN with density functional theory and investigate the dynamics of specific energy bands with a simple two-band model. Finally, we find that laser-induced intraband transitions play a significant role in the transient absorption even for the two-dimensional material and that the nonadiabatic features are induced by the dynamical Franz–Keldysh effect with an anomalous band dispersion.

Signatures of a Conical Intersection in Attosecond Transient Absorption Spectroscopy.

We characterize attosecond transient absorption spectroscopy (ATAS) in molecules with coupled nuclear and electronic dynamics in the vicinity of a conical intersection between adiabatic potential energy surfaces. With respect to ATAS, the nonadiabatic vibronic coupling strength can be divided into weak, intermediate, and strong, and the characteristics of spectra belonging to each of these domains are discussed. The results can guide the analysis of ATAS experiments in molecules with conical intersections.

Attosecond optical-field-enhanced carrier injection into the GaAs conduction band

Resolving the fundamental carrier dynamics induced in solids by strong electric fields is essential for future applications, ranging from nanoscale transistors1,2 to high-speed electro-optical switches3. How fast and at what rate can electrons be injected into the conduction band of a solid? Here, we investigate the sub-femtosecond response of GaAs induced by resonant intense near-infrared laser pulses using attosecond transient absorption spectroscopy. In particular, we unravel the distinct role of intra- versus interband transitions. Surprisingly, we found that despite the resonant driving laser, the optical response during the light–matter interaction is dominated by intraband motion. Furthermore, we observed that the coupling between the two mechanisms results in a significant enhancement of the carrier injection from the valence into the conduction band. This is especially unexpected as the intraband mechanism itself can accelerate carriers only within the same band. This physical phenomenon could be used to control ultrafast carrier excitation and boost injection rates in electronic switches in the petahertz regime. Significant enhancement of carrier injection into the conduction band is observed for GaAs subjected to intense resonant near-infrared laser pumping. Attosecond-resolved investigation reveals the interplay between the intra- and interband transitions.

Attosecond transient absorption spectroscopy: Comparative study based on three-level modeling**Project supported by the National Natural Science Foundation of China (Grant Nos. 11674034 and 11564033) and the Foundation of President of the China Academy of Engineering Physics (Grant No. 2014-1-029).

In the present paper, the time-resolved transient absorption spectroscopy of helium atoms is investigated based on the three-level modeling. The helium atoms are subjected to an extreme ultraviolet (XUV) attosecond pulse and a time-delayed infrared (IR) few-cycle laser field. The odd excited state are populated from the ground state by the XUV pulse due to the dipole selection rule, and probed by the time-delayed IR laser. The time-resolved transient absorption spectroscopy based on the different coupling mechanism demonstrate some different features, the photoabsorption spectrum based on three-level model with rotating wave approximation (RWA) cannot repeat the fast oscillation and the sideband structure which have been observed in the previous experimental investigation. The dressing effect of IR laser pulse on the ground state can contribute new interference structures in the photoabsorption spectrum.

Analytic modeling of structures in attosecond transient-absorption spectra

Attosecond transient-absorption spectroscopy (ATAS) is an established method for exploring electron dynamics on the subfemtosecond time-scale. ATAS spectra contain certain ubiquitous features, such as oscillating fringes, light-induced structures and hyperbolic sidebands, representing physical processes. We derive closed analytical expressions describing these features, based on a three-level system responding adiabatically to the influence of an infrared field in conjunction with an extreme ultraviolet pulse, and use He to illustrate the theory. The validity of the formulas is substantiated by comparing their predictions with spectra calculated numerically by the time-dependent Schr\"odinger equation. The closed analytical forms and the details of their derivation resolve the origins of the features.

Attosecond transient absorption spectroscopy of helium above the N=2 ionization threshold

Attosecond transient absorption spectroscopy (ATAS) allows for the study of electron dynamics in atoms and molecules with attosecond time resolution. Previous works reported in the literature have made use of ATAS to image and control such dynamics in the single-channel ionization continuum of helium; in particular, in the vicinity of the doubly excited autoionizing states lying between the $N=1$ and $N=2$ thresholds. In this work, we have extended these studies to autoionizing states lying above the $N=2$ threshold, where several ionization channels are open. From an accurate solution of the time-dependent Schr\odinger equation, we predict the appearance of pronounced one-photon beatings between the $3snp$ states and the adjacent ${}^{1}{S}^{e}$ and ${}^{1}{D}^{e}$ resonances, as well as, more surprisingly, two-photon beatings between the $3s3p$ doubly excited state and the ${}^{1}{P}^{o}$ nonresonant continuum. Both effects lead to a significant distortion of the $3snp$ Fano profiles and to a strong variation of these profiles with the pump-probe delay, thus demonstrating control of the corresponding multichannel two-electron correlated wave packets, in the same way as reported for resonances lying below the $N=2$ threshold.

Attosecond counter-rotating-wave effect in xenon driven by strong fields

We investigate the subfemtosecond dynamics of a highly excited xenon atom coherently driven by a strong control field at which the Rabi frequency of the system is comparable to the frequency of a driving laser. The widely used rotating-wave approximation breaks down at such fields, resulting in features such as the counter-rotating-wave (CRW) effect. We present a time-resolved observation of the CRW effect in the highly excited $4{d}^{\ensuremath{-}1}np$ xenon using attosecond transient absorption spectroscopy. Time-dependent many-body theory confirms the observation and explains the various features of the absorption spectrum seen in experiment.

Correlation-driven charge migration following double ionization and attosecond transient absorption spectroscopy

We theoretically investigate charge migration following prompt double ionization. Thereby, we extend the concept of correlation-driven charge migration, which was introduced by Cederbaum and coworkers for single ionization [Chem. Phys. Lett. 307, 205 (1999)], to doubly ionized molecules. This allows us to demonstrate that compared to singly ionized molecules, in multiply ionized molecules, electron dynamics originating from electronic relaxation and correlation are particularly prominent. In addition, we also discuss how these correlation-driven electron dynamics might be evidenced and traced experimentally using attosecond transient absorption spectroscopy. For this purpose, we determine the time-resolved absorption cross section and find that the correlated electron dynamics discussed are reflected in it with exceptionally great detail. Strikingly, we find that features in the cross section can be traced back to electron hole populations and time-dependent partial charges and hence, can be interpreted with surprising ease. By taking advantage of element-specific core-to-valence transitions even atomic spatial resolution can be achieved. Thus, with the theoretical considerations presented, not only do we predict particularly diverse and correlated electron dynamics in molecules to follow prompt multiple ionization but we also identify a promising route towards their experimental investigation.

Attosecond transient-absorption dynamics of xenon core-excited states in a strong driving field

Attosecond transient absorption spectroscopy of xenon atoms is performed using near-infrared fields well into the tunneling region, providing insight into the ultrafast control of material optical properties in the strongly driven regime.

State-resolved attosecond reversible and irreversible dynamics in strong optical fields

Strong-field ionization (SFI) is a key process for accessing real-time quantum dynamics of electrons on the attosecond timescale. The theoretical foundation of SFI was pioneered in the 1960s, and later refined by various analytical models. While asymptotic ionization rates predicted by these models have been tested to be in reasonable agreement for a wide range of laser parameters, predictions for SFI on the sub-laser-cycle timescale are either beyond the scope of the models or show strong qualitative deviations from full quantum-mechanical simulations. Here, using the unprecedented state specificity of attosecond transient absorption spectroscopy, we follow the real-time SFI process of the two valence spin–orbit states of xenon. The results reveal that the irreversible tunnelling contribution is accompanied by a reversible electronic population that exhibits an observable spin–orbit-dependent phase delay. A detailed theoretical analysis attributes this observation to transient ground-state polarization, an unexpected facet of SFI that cannot be captured by existing analytical models that focus exclusively on the production of asymptotic electron/ion yields. An experimental and theoretical study of the real-time dynamics in strong-field ionization of xenon atoms reveals the previously unknown role of transient ground-state polarization.

Core-level attosecond transient absorption spectroscopy of laser-dressed solid films of Si and Zr

We investigated experimentally as well as theoretically the ultrafast response of the wave function of the conduction band (CB) of Si and Zr to a near-infrared laser field using extreme ultraviolet (XUV) absorption spectroscopy in the spectral range of 80--220 eV. The measured dynamics of the XUV transmission demonstrates that the wave function of the CB follows the electric field of the dressing laser pulse. In these terms, laser dressing was earlier mainly studied on gases. Measurements with two-femtosecond and 200-attosecond temporal steps were performed in the vicinity of the $\mathrm{Si}\phantom{\rule{0.16em}{0ex}}{L}_{2,3}$ edge near 100 eV, the $\mathrm{Si}\phantom{\rule{0.16em}{0ex}}{L}_{1}$ edge near 150 eV, and the $\mathrm{Zr}\phantom{\rule{0.16em}{0ex}}{M}_{4,5}$ edge near 180 eV. The observed changes were dependent on the core states being excited by the XUV probe pulse. At the $2p$ to CB transitions of Si, the XUV transmission increased via the effect of the dressing laser pulse, while at the $2s$ to CB transition of Si and the $3d$ to CB transition of Zr, the XUV transmission decreased. Furthermore, beats between the transition from $2{p}_{1/2}$ and $2{p}_{3/2}$ levels of Si and from $3{d}_{3/2}$ and $3{d}_{5/2}$ levels of Zr were observed with 20.7 fs and 3.6 fs periods.