arXiv subjects

Jon P. Marangos

Publications and source records attributed to Jon P. Marangos.

17 recordsLinked to original sources

arXiv2026

Pulse-Duration Control of Subcycle Multiband Electron Dynamics Extends the High-Harmonic Cutoff in a Light-Driven Insulator

We demonstrate pathway-selective control of extreme-ultraviolet high-harmonic generation by jointly tuning laser pulse duration ($5$ - $29$ fs) and intensity ($0.8$ - $74$ TW/cm$^2$). Many-cycle pulses at moderate intensities, $\sim 6$ TW/cm$^2$, promote cumulative carrier transfer over successive optical cycles, progressively accessing higher conduction bands. In contrast, few-cycle, high-intensity, $\sim 22$ TW/cm$^2$, pulses drive subcycle multiband dynamics that reach $25$ - $50$ eV photon energies before decoherence can suppress coherent emission. These results reveal pulse duration and intensity as decisive control knobs for high-harmonic emission, opening a route to band-structure-guided pulse design for higher energy extreme-ultraviolet light sources.

physics.optics↗

arXiv2026

Attosecond soft X-ray pulses generated by chirp-dispersed manipulation in an XFEL reveal nonlinear core-electron dynamics in neon

Free-electron lasers have demonstrated their capability of generating intense attosecond X-ray pulses, which are the key to studying electron dynamics at their natural time scale and in specifically targeted electronic states, but come at the expanse of complicated generation schemes and stochastic pulse shapes. Here, we demonstrate a novel and simple operation concept based on the manipulation of the electron-bunch chirp-dispersion and working with the full 4.5 MHz repetition rate at the European XFEL in Germany. With a high-fidelity single-shot temporal characterisation, we detect X-ray pulses with durations of down to 200 attoseconds and peak powers reaching into the terawatt regime at ~1 keV photon energy. As a direct application, we present simultaneous measurements of nonlinear X-ray-matter interaction via time-resolved electron spectroscopy. Using the derived temporal pulse information and restricting the durations to a regime where individual X-ray pulses are shorter than the single-core-hole life time in neon atoms, we reveal an otherwise hidden peak-intensity dependence in the nonlinear dynamics of double-core-hole formation. Our results open the field of attosecond science to the investigation of electronic processes not only in the ground state but also in systems driven far off their equilibrium. They shed light on highly transient intermediate steps in complex electronic dynamics and thus promise to help build the conceptual bridge between fundamental physical processes and chemical photo-reactions.

physics.optics↗

arXiv2026

Roadmap on Attosecond Science

Twenty-five years have passed since the first experimental demonstration of attosecond pulses, marking the advent of our ability to resolve and control electron motion in real time. What began as a technological breakthrough - generating the shortest flashes ever produced - has evolved into a powerful approach for probing and steering electronic dynamics in atoms, molecules, and solids. This roadmap, authored by leading experts in the field, surveys the recent rapid progress in the generation and characterization of attosecond pulses, emerging attosecond measurement and control techniques, and their expanding range of applications. It reviews current and future developments in attosecond light sources, including novel laser technologies, waveform synthesizers, new schemes for high-order harmonic generation, attosecond pulse generation at free-electron lasers, and structured light. Advances in attosecond measurement methodologies are also discussed, encompassing all-attosecond pump-probe spectroscopy, attosecond four-wave mixing, attosecond microscopy, spectroscopy with light transients, and attosecond interferometry. Furthermore, the roadmap addresses applications of attosecond spectroscopy to reveal electron dynamics in molecules and condensed matter systems from both theoretical and experimental perspectives, and highlights emerging directions at the interface with quantum optics and quantum entanglement. Overall, this work aims to serve as a comprehensive resource for navigating the evolving landscape of attosecond science.

physics.optics↗

arXiv2024

Attosecond Coherent Electron Motion in a Photoionized Aromatic Molecule

In molecular systems, the ultrafast motion of electrons initiates the process of chemical change. Tracking this electronic motion across molecules requires coupling attosecond time resolution to atomic-scale spatial sensitivity. In this work, we employ a pair of attosecond x-ray pulses from an x-ray free-electron laser to follow electron motion resulting from the sudden removal of an electron from a prototypical aromatic system, para-aminophenol. X-ray absorption enables tracking this motion with atomic-site specificity. Our measurements are compared with state-of-the-art computational modeling, reproducing the observed response across multiple timescales. Sub-femtosecond dynamics are assigned to states undergoing non-radiative decay, while few-femtosecond oscillatory motion is associated with electronic wavepacket motion in stable cation states, that will eventually couple to nuclear motion. Our work provides insight on the ultrafast charge motion preceding and initiating chemical transformations in moderately complex systems, and provides a powerful benchmark for computational models of ultrafast charge motion in matter.

physics.chem-ph↗

arXiv2024

Signature of attochemical quantum interference upon ionization and excitation of an electronic wavepacket in fluoro-benzene

Ultrashort pulses can excite or ionize molecules and populate coherent electronic wavepackets, inducing complex dynamics. In this work, we simulate the coupled electron-nuclear dynamics upon ionization to different electronic wavepackets of (deuterated) benzene and fluoro-benzene molecules, quantum mechanically and in full dimensionality. In fluoro-benzene, the calculations unravel both inter-state and intra-state quantum interferences that leave clear signatures of attochemistry and charge-directed dynamics in the shape of the autocorrelation function. The latter are in agreement with experimental high harmonic spectroscopy measurements of benzenes and fluoro-benzene.

physics.chem-ph↗

arXiv2024

Ultrafast Broadband Strong-Field Tunnelling in Asymmetric Nanogaps for Time-Resolved Nanoscopy

Femtosecond-fast and nanometre-size pulses of electrons are emerging as unique probes for ultrafast dynamics at the nanoscale. Presently, such pulses are achievable only in highly sophisticated ultrafast electron microscopes or equally complex setups involving few-cycle-pulsed lasers with stable carrier-envelope phase (CEP) and nanotip probes. Here, we show that the generation of femtosecond pulses of nanoscale tunnelling electrons can be achieved in any ultrafast optical laboratory, using any (deep-UV to mid-IR) femtosecond laser in combination with photosensitive asymmetric nanogap (PAN) diodes fabricated via easy-to-scale adhesion lithography. The dominant mechanism producing tunnelling electrons in PANs is strong-field emission, which is easily achievable without CEP locking or external bias voltage. We employ PANs to demonstrate ultrafast nanoscopy of metal-halide perovskite quantum dots immobilised inside a 10-nm Al/Au nanogap and to characterise laser pulses across the entire optical region (266-6700 nm). Short electron pulses in PANs open the way towards scalable on-chip femtosecond electron measurements and novel design approaches for integrated ultrafast sensing nanodevices.

physics.optics↗

arXiv2024

Efficient prediction of attosecond two-colour pulses from an X-ray free-electron laser with machine learning

X-ray free-electron lasers are sources of coherent, high-intensity X-rays with numerous applications in ultra-fast measurements and dynamic structural imaging. Due to the stochastic nature of the self-amplified spontaneous emission process and the difficulty in controlling injection of electrons, output pulses exhibit significant noise and limited temporal coherence. Standard measurement techniques used for characterizing two-coloured X-ray pulses are challenging, as they are either invasive or diagnostically expensive. In this work, we employ machine learning methods such as neural networks and decision trees to predict the central photon energies of pairs of attosecond fundamental and second harmonic pulses using parameters that are easily recorded at the high-repetition rate of a single shot. Using real experimental data, we apply a detailed feature analysis on the input parameters while optimizing the training time of the machine learning methods. Our predictive models are able to make predictions of central photon energy for one of the pulses without measuring the other pulse, thereby leveraging the use of the spectrometer without having to extend its detection window. We anticipate applications in X-ray spectroscopy using XFELs, such as in time-resolved X-ray absorption and photoemission spectroscopy, where improved measurement of input spectra will lead to better experimental outcomes.

physics.acc-ph↗

arXiv2024

Attosecond Delays in X-ray Molecular Ionization

The photoelectric effect is not truly instantaneous, but exhibits attosecond delays that can reveal complex molecular dynamics. Sub-femtosecond duration light pulses provide the requisite tools to resolve the dynamics of photoionization. Accordingly, the past decade has produced a large volume of work on photoionization delays following single photon absorption of an extreme ultraviolet (XUV) photon. However, the measurement of time-resolved core-level photoionization remained out of reach. The required x-ray photon energies needed for core-level photoionization were not available with attosecond tabletop sources. We have now measured the x-ray photoemission delay of core-level electrons, and here report unexpectedly large delays, ranging up to 700 attoseconds in NO near the oxygen K-shell threshold. These measurements exploit attosecond soft x-ray pulses from a free-electron laser (XFEL) to scan across the entire region near the K-shell threshold. Furthermore, we find the delay spectrum is richly modulated, suggesting several contributions including transient trapping of the photoelectron due to shape resonances, collisions with the Auger-Meitner electron that is emitted in the rapid non-radiative relaxation of the molecule, and multi-electron scattering effects. The results demonstrate how x-ray attosecond experiments, supported by comprehensive theoretical modelling, can unravel the complex correlated dynamics of core-level photoionization.

physics.atom-ph↗

arXiv2024

Experimental Demonstration of Attosecond Pump-Probe Spectroscopy with an X-ray Free-Electron Laser

Pump-probe experiments with sub-femtosecond resolution are the key to understanding electronic dynamics in quantum systems. Here we demonstrate the generation and control of sub-femtosecond pulse pairs from a two-colour X-ray free-electron laser (XFEL). By measuring the delay between the two pulses with an angular streaking diagnostic, we characterise the group velocity of the XFEL and demonstrate control of the pulse delay down to 270 as. We demonstrate the application of this technique to a pump-probe measurement in core-excited para-aminophenol. These results demonstrate the ability to perform pump-probe experiments with sub-femtosecond resolution and atomic site specificity.

physics.acc-ph↗

arXiv2024

Coupled Electron-Nuclear Dynamics Induced and Monitored with Femtosecond Soft X-ray Pulses in the Amino Acid Glycine

The coupling of electronic and nuclear motion in polyatomic molecules is at the heart of attochemistry. The molecular properties, transient structures and reaction mechanism of these many-body quantum objects are defined on the level of electrons and ions by molecular wave functions and their coherent superposition, respectively. In the present contribution we monitor nonadiabatic quantum wave packet dynamics during molecular charge motion by reconstructing both, the oscillatory charge density distribution and the characteristic time-dependent nuclear configuration coordinate from time-resolved Auger electron spectroscopic data recorded in previous studies on glycine molecules [Sci. Adv. 2022, 8, eabn6848]. The electronic and nuclear motion on the femtosecond timescale was induced and probed in kinematically complete soft x-ray experiments at the FLASH free-electron laser facility. The detailed analysis of amplitude, instantaneous phase and instantaneous frequency of the propagating many-body wave packet during its lifecycle provides unprecedented insight into dynamical processes beyond the Born-Oppenheimer approximation. We are confident that the refined experimental data evaluation helps to develop new theoretical tools to describe time-dependent molecular wave functions in complicated, but ubiquitous, non-Born-Oppenheimer photochemical conditions.

physics.chem-ph↗

arXiv2022

Electronic Quantum Coherence in Glycine Molecules Probed with Ultrashort X-ray Pulses in Real Time

Quantum coherence between electronic states of a photoionized molecule and the resulting process of ultrafast electron-hole migration have been put forward as a possible quantum mechanism of charge-directed reactivity governing the photoionization-induced molecular decomposition. Attosecond experiments based on the indirect (fragment ion-based) characterization of the proposed electronic phenomena suggest that the photoionization-induced electronic coherence can survive for tens of femtoseconds, while some theoretical studies predict much faster decay of the coherence due to the quantum uncertainty in the nuclear positions and the nuclear-motion effects. The open questions are: do long-lived electronic quantum coherences exist in complex molecules and can they be probed directly, i.e. via electronic observables? Here, we use x-rays both to create and to directly probe quantum coherence in the photoionized amino acid glycine. The outgoing photoelectron wave leaves behind a positively charged ion that is in a coherent superposition of quantum mechanical eigenstates lying within the ionizing pulse spectral bandwidth. Delayed x-ray pulses track the induced coherence through resonant x-ray absorption that induces Auger decay and by the photoelectron emission from sequential double photoionization. Sinusoidal temporal modulation of the detected signal at early times (0 - 25 fs) is observed in both measurements. Advanced ab initio many-electron simulations, taking into account the quantum uncertainty in the nuclear positions, allow us to explain the first 25 fs of the detected coherent quantum evolution in terms of the electronic coherence.

physics.chem-ph↗

arXiv2021

Attosecond Coherent Electron Motion in Auger-Meitner Decay

In quantum systems, coherent superpositions of electronic states evolve on ultrafast timescales (few femtosecond to attosecond, 1 as = 0.001 fs = 10^{-18} s), leading to a time dependent charge density. Here we exploit the first attosecond soft x-ray pulses produced by an x-ray free-electron laser to induce a coherent core-hole excitation in nitric oxide. Using an additional circularly polarized infrared laser pulse we create a clock to time-resolve the electron dynamics, and demonstrate control of the coherent electron motion by tuning the photon energy of the x-ray pulse. Core-excited states offer a fundamental test bed for studying coherent electron dynamics in highly excited and strongly correlated matter.

physics.chem-ph↗

arXiv2020

Two-dimensional partial covariance mass spectrometry for the top-down analysis of intact proteins

Two-dimensional partial covariance mass spectrometry (2D-PC-MS) exploits the inherent fluctuations of fragment ion abundances across a series of tandem mass spectra, to identify correlated pairs of fragment ions produced along the same fragmentation pathway of the same parent (e.g. peptide) ion. Here, we apply 2D-PC-MS to the analysis of intact protein ions in a standard linear ion trap mass analyzer, using the fact that the fragment-fragment correlation signals are much more specific to bio-molecular sequence than 1D MS/MS signals at the same mass accuracy and resolution. We show that from the distribution of signals on a 2D-PC-MS map it is possible to extract the charge state of both parent and fragment ions without resolving the isotopic envelope. Furthermore, the 2D map of fragment-fragment correlations naturally reveals the secondary decomposition pathways of the fragment ions. We access this spectral information using an adapted version of the Hough transform. We demonstrate the successful identification of highly charged, intact protein molecules without the need for high mass resolution. Using this technique we also perform the in silico deconvolution of the overlapping fragment ion signals from two co-isolated and co-fragmented intact protein molecules, demonstrating a viable new method for the concurrent mass spectrometric identification of a mixture of intact protein ions from the same fragment ion spectrum.

physics.chem-ph↗

arXiv2019

Attosecond Transient Absorption Spooktroscopy: a ghost imaging approach to ultrafast absorption spectroscopy

The recent demonstration of isolated attosecond pulses from an X-ray free-electron laser (XFEL) opens the possibility for probing ultrafast electron dynamics at X-ray wavelengths. An established experimental method for probing ultrafast dynamics is X-ray transient absorption spectroscopy, where the X-ray absorption spectrum is measured by scanning the central photon energy and recording the resultant photoproducts. The spectral bandwidth inherent to attosecond pulses is wide compared to the resonant features typically probed, which generally precludes the application of this technique in the attosecond regime. In this paper we propose and demonstrate a new technique to conduct transient absorption spectroscopy with broad bandwidth attosecond pulses with the aid of ghost imaging, recovering sub-bandwidth resolution in photoproduct-based absorption measurements.

physics.chem-ph↗

arXiv2019

Partial covariance two-dimensional mass spectrometry for determination of biomolecular primary structure

Mass spectrometry (MS) is used widely in biomolecular structural analysis and is particularly dominant in the study of proteins. Despite its considerable power, state-of-the-art protein MS frequently suffers from limited reliability of spectrum-to-structure assignments. This could not be solved fully by the dramatic increase in mass accuracy and resolution of modern MS instrumentation or by the introduction of new fragmentation methods. Here we present a new kind of two-dimensional mass spectrometry for high fidelity determination of a biomolecular primary structure based on partial covariance mapping. Partial covariance two-dimensional mass spectrometry (pC-2DMS) detects intrinsic statistical correlations between biomolecular fragments originating from the same or consecutive decomposition events. This enables identification of pairs of ions produced along the same fragmentation pathway of a biomolecule across its entire fragment mass spectrum. We demonstrate that the fragment-fragment correlations revealed by pC-2DMS provide much more specific information on the amino acid sequence and its covalent modifications than the individual fragment mass-to-charge ratios on which standard one-dimensional MS is based. We illustrate the power of pC-2DMS by using it to resolve structural isomers of combinatorially modified histone peptides inaccessible to standard MS.

physics.chem-ph↗

arXiv2019

Direct characterisation of tuneable few-femtosecond dispersive-wave pulses in the deep UV

Dispersive wave emission (DWE) in gas-filled hollow-core dielectric waveguides is a promising source of tuneable coherent and broadband radiation, but so far the generation of few-femtosecond pulses using this technique has not been demonstrated. Using in-vacuum frequency-resolved optical gating, we directly characterise tuneable 3fs pulses in the deep ultraviolet generated via DWE. Through numerical simulations, we identify that the use of a pressure gradient in the waveguide is critical for the generation of short pulses.

physics.optics↗

arXiv2000

Prospects for photon blockade in four level systems in the N configuration with more than one atom

We show that for appropriate choices of parameters it is possible to achieve photon blockade in idealised one, two and three atom systems. We also include realistic parameter ranges for rubidium as the atomic species. Our results circumvent the doubts cast by recent discussion in the literature (Grangier et al Phys. Rev Lett. 81, 2833 (1998), Imamoglu et al Phys. Rev. Lett. 81, 2836 (1998)) on the possibility of photon blockade in multi-atom systems.

quant-ph↗