Pulse overlap ambiguities in multiple quantum coherence spectroscopy.

Coherent two-dimensional electronic spectroscopy probes ultrafast dynamics using femtosecond pulses. In the case where the time scale of the studied dynamics become comparable to the pulse duration, pulse overlap effects may compromise the experimental data. Here, we perform one-dimensional coherence scans and study pulse overlap effects in clean two-level systems. We find parasitic multiple-quantum coherences as a consequence of the arbitrary time ordering during the temporal pulse overlap. Surprisingly, the coherence lifetimes exceed the pulse coherence time by a factor of 1.85. These findings have important implications for the interpretation of higher-order coherent two-dimensional and related spectroscopy experiments.

Two-dimensional electronic spectroscopy of an ultracold gas.

Femtosecond coherent multidimensional spectroscopy is demonstrated for an ultracold gas.  A setup for phase modulation spectroscopy is used to probe the 32S1/2-22P1/2,3/2 transition in an 800µK-cold sample of 7Li atoms confined in a magneto-optical trap. The observation of a double quantum coherence response, a signature of interparticle interactions, paves the way for detailed investigations of few- and many-body effects in ultracold gases using this technique. The experiment combines a frequency resolution of 3 GHz with a potential time resolution of 200 fs, which allows for high-resolution studies of ultracold atoms and molecules both in the frequency and in the time domain.

Generation and compression of 10-fs deep ultraviolet pulses at high repetition rate using standard optics: erratum.

We present an erratum regarding the calculated phase matching bandwidths for achromatic second harmonic generation presented in our paper [Opt. Express29, 25593 (2021)10.1364/OE.425053].

Extreme Ultraviolet Wave Packet Interferometry of the Autoionizing HeNe Dimer.

Femtosecond extreme ultraviolet wave packet interferometry (XUV-WPI) was applied to study resonant interatomic Coulombic decay (ICD) in the HeNe dimer. The high demands on phase stability and sensitivity for vibronic XUV-WPI of molecular-beam targets are met using an XUV phase-cycling scheme. The detected quantum interferences exhibit vibronic dephasing and rephasing signatures along with an ultrafast decoherence assigned to the ICD process. A Fourier analysis reveals the molecular absorption spectrum with high resolution. The demonstrated experiment shows a promising route for the real-time analysis of ultrafast ICD processes with both high temporal and high spectral resolution.

High-resolution two-dimensional electronic spectroscopy reveals the homogeneous line profile of chromophores solvated in nanoclusters.

Doped clusters in the gas phase provide nanoconfined model systems for the study of system-bath interactions. To gain insight into interaction mechanisms between chromophores and their environment, the ensemble inhomogeneity has to be lifted and the homogeneous line profile must be accessed. However, such measurements are very challenging at the low particle densities and low signal levels in cluster beam experiments. Here, we dope cryogenic rare-gas clusters with phthalocyanine molecules and apply action-detected two-dimensional electronic spectroscopy to gain insight into the local molecule-cluster environment for solid and superfluid cluster species. The high-resolution homogeneous linewidth analysis provides a benchmark for the theoretical modelling of binding configurations and shows a promising route for high-resolution molecular two-dimensional spectroscopy.

Time-Resolved Ultrafast Interatomic Coulombic Decay in Superexcited Sodium-Doped Helium Nanodroplets.

The autoionization dynamics of superexcited superfluid He nanodroplets doped with Na atoms is studied by extreme-ultraviolet (XUV) time-resolved electron spectroscopy. Following excitation into the higher-lying droplet absorption band, the droplet relaxes into the lowest metastable atomic 1s2s 1,3S states from which interatomic Coulombic decay (ICD) takes place either between two excited He atoms or between an excited He atom and a Na atom attached to the droplet surface. Four main ICD channels are identified, and their decay times are determined by varying the delay between the XUV pulse and a UV pulse that ionizes the initial excited state and thereby quenches ICD. The decay times for the different channels all fall in the range of ∼1 ps, indicating that the ICD dynamics are mainly determined by the droplet environment. A periodic modulation of the transient ICD signals is tentatively attributed to the oscillation of the bubble forming around the localized He excitation.

Changes in Endocan and Dermatan Sulfate Are Associated with Biomechanical Properties of Abdominal Aortic Wall during Aneurysm Expansion and Rupture.

BACKGROUND AND AIMS: The study aimed to assess the potential of proteoglycans (PGs) and collagens as serological biomarkers in the abdominal aortic aneurysm (AAA). Furthermore, we investigated the underlying mechano-biological interactions and signaling pathways. METHODS: Tissue and serum samples from patients with ruptured AAA (rAAA; n = 29), elective AAA (eAAA; n = 78), and healthy individuals (n = 8) were evaluated by histology, immunohistochemistry, and enzyme-linked immunosorbent assay, and mechanical properties were assessed by tensile tests. Regulatory pathways were determined by membrane-based sandwich immunoassay. RESULTS: In AAA samples, collagen type I and III (Col1 and Col3), chondroitin sulfate, and dermatan sulfate (DS) were significantly increased compared with controls (3.0-, 3.2-, 1.3-, and 53-fold; p < 0.01). Col1 and endocan were also elevated in the serum of AAA patients (3.6- and 6.0-fold; p < 0.01), while DS was significantly decreased (2.5-fold; p < 0.01). Histological scoring showed increased total PGs and focal accumulation in rAAA compared with eAAA. Tissue ß-stiffness was higher in rAAA compared with eAAA (2.0-fold, p = 0.02). Serum Col1 correlated with maximum tensile force and failure tension (r = 0.448 and 0.333; p < 0.01, and r = 0.02), tissue endocan correlated with α-stiffness (r = 0.340; p < 0.01). Signaling pathways in AAA were associated with extracellular matrix synthesis and vascular smooth muscle cell proliferation. In particular, Src family kinases and platelet-derived growth factor- and epidermal growth factor-related proteins seem to be involved. CONCLUSION: Our findings reveal a structural association between collagen and PGs and their response to changes in mechanical loads in AAA. Particularly Col1 and endocan reflect the mechano-biological conditions of the aortic wall also in the patient's serum and might serve for AAA risk stratification.

Generation and compression of 10-fs deep ultraviolet pulses at high repetition rate using standard optics.

The generation and characterization of ultrashort laser pulses in the deep ultraviolet spectral region is challenging, especially at high pulse repetition rates and low pulse energies. Here, we combine achromatic second harmonic generation and adaptive pulse compression for the efficient generation of sub-10 fs deep ultraviolet laser pulses at a laser repetition rate of 200 kHz. Furthermore, we simplify the pulse compression scheme and reach pulse durations of ≈10 fs without the use of adaptive optics. We demonstrate straight-forward tuning from 250 to 320 nm, broad pulse spectra of up to 63 nm width, excellent stability and a high robustness against misalignment. These features make the approach appealing for numerous spectroscopy and imaging applications.

Unravelling the full relaxation dynamics of superexcited helium nanodroplets.

The relaxation dynamics of superexcited superfluid He nanodroplets is thoroughly investigated by means of extreme-ultraviolet (XUV) femtosecond electron and ion spectroscopy complemented by time-dependent density functional theory (TDDFT). Three main paths leading to the emission of electrons and ions are identified: droplet autoionization, pump-probe photoionization, and autoionization induced by re-excitation of droplets relaxing into levels below the droplet ionization threshold. The most abundant product ions are He2+, generated by droplet autoionization and by photoionization of droplet-bound excited He atoms. He+ appear with some pump-probe delay as a result of the ejection He atoms in their lowest excited states from the droplets. The state-resolved time-dependent photoelectron spectra reveal that intermediate excited states of the droplets are populated in the course of the relaxation, terminating in the lowest-lying metastable singlet and triplet He atomic states. The slightly faster relaxation of the triplet state compared to the singlet state is in agreement with the simulation showing faster formation of a bubble around a He atom in the triplet state.

Biomechanical rupture risk assessment of abdominal aortic aneurysms using clinical data: A patient-specific, probabilistic framework and comparative case-control study.

We present a data-informed, highly personalized, probabilistic approach for the quantification of abdominal aortic aneurysm (AAA) rupture risk. Our novel framework builds upon a comprehensive database of tensile test results that were carried out on 305 AAA tissue samples from 139 patients, as well as corresponding non-invasively and clinically accessible patient-specific data. Based on this, a multivariate regression model is created to obtain a probabilistic description of personalized vessel wall properties associated with a prospective AAA patient. We formulate a probabilistic rupture risk index that consistently incorporates the available statistical information and generalizes existing approaches. For the efficient evaluation of this index, a flexible Kriging-based surrogate model with an active training process is proposed. In a case-control study, the methodology is applied on a total of 36 retrospective, diameter matched asymptomatic (group 1, n = 18) and known symptomatic/ruptured (group 2, n = 18) cohort of AAA patients. Finally, we show its efficacy to discriminate between the two groups and demonstrate competitive performance in comparison to existing deterministic and probabilistic biomechanical indices.

High-gain harmonic generation with temporally overlapping seed pulses and application to ultrafast spectroscopy.

Collinear double-pulse seeding of the High-Gain Harmonic Generation (HGHG) process in a free-electron laser (FEL) is a promising approach to facilitate various coherent nonlinear spectroscopy schemes in the extreme ultraviolet (XUV) spectral range. However, in collinear arrangements using a single nonlinear medium, temporally overlapping seed pulses may introduce nonlinear mixing signals that compromise the experiment at short time delays. Here, we investigate these effects in detail by extending the analysis described in a recent publication (Wituschek et al., Nat. Commun., 11, 883, 2020). High-order fringe-resolved autocorrelation and wave packet interferometry experiments at photon energies > 23 eV are performed, accompanied by numerical simulations. It turns out that both the autocorrelation and the wave-packet interferometry data are very sensitive to saturation effects and can thus be used to characterize saturation in the HGHG process. Our results further imply that time-resolved spectroscopy experiments are feasible even for time delays smaller than the seed pulse duration.

Effects of high pulse intensity and chirp in two-dimensional electronic spectroscopy of an atomic vapor.

The effects of high pulse intensity and chirp on two-dimensional electronic spectroscopy signals are experimentally investigated in the highly non-perturbative regime using atomic rubidium vapor as clean model system. Data analysis is performed based on higher-order Feynman diagrams and non-perturbative numerical simulations of the system response. It is shown that higher-order contributions may lead to a fundamental change of the static appearance and beating-maps of the 2D spectra and that chirped pulses enhance or suppress distinct higher-order pathways. We further give an estimate of the threshold intensity beyond which the high-intensity effects become visible for the system under consideration.

Tracking attosecond electronic coherences using phase-manipulated extreme ultraviolet pulses.

The recent development of ultrafast extreme ultraviolet (XUV) coherent light sources bears great potential for a better understanding of the structure and dynamics of matter. Promising routes are advanced coherent control and nonlinear spectroscopy schemes in the XUV energy range, yielding unprecedented spatial and temporal resolution. However, their implementation has been hampered by the experimental challenge of generating XUV pulse sequences with precisely controlled timing and phase properties. In particular, direct control and manipulation of the phase of individual pulses within an XUV pulse sequence opens exciting possibilities for coherent control and multidimensional spectroscopy, but has not been accomplished. Here, we overcome these constraints in a highly time-stabilized and phase-modulated XUV-pump, XUV-probe experiment, which directly probes the evolution and dephasing of an inner subshell electronic coherence. This approach, avoiding any XUV optics for direct pulse manipulation, opens up extensive applications of advanced nonlinear optics and spectroscopy at XUV wavelengths.

Stable interferometric platform for phase modulation of seeded free-electron lasers.

We present a compact phase modulation setup designed for high laser intensities sufficient to drive highly nonlinear processes, such as high-gain harmonic generation in seeded free-electron lasers. This paves the way for all-extreme-ultravioloet coherent nonlinear spectroscopy. The high linearity, phase stability, and sensitivity of the setup are demonstrated by probing the quantum interference of electronic wave packets in the deep ultraviolet region (268 nm) combined with photoion time-of-flight mass spectrometry.

Delocalized excitons and interaction effects in extremely dilute thermal ensembles.

Long-range interparticle interactions are revealed in extremely dilute thermal atomic ensembles using highly sensitive nonlinear femtosecond spectroscopy. Delocalized excitons are detected in the atomic systems at particle densities where the mean interatomic distance (>10 µm) is much greater than the laser wavelength and multi-particle coherences should destructively interfere over the ensemble average. With a combined experimental and theoretical analysis, we identify an effective interaction mechanism, presumably of dipolar nature, as the origin of the excitonic signals. Our study implies that even in highly-dilute thermal atom ensembles, significant transition dipole-dipole interaction networks may form that require advanced modeling beyond the nearest neighbor approximation to quantitatively capture the details of their many-body properties.

Coherent multidimensional spectroscopy of dilute gas-phase nanosystems.

Two-dimensional electronic spectroscopy (2DES) is one of the most powerful spectroscopic techniques with unique sensitivity to couplings, coherence properties and real-time dynamics of a quantum system. While successfully applied to a variety of condensed phase samples, high precision experiments on isolated systems in the gas phase have been so far precluded by insufficient sensitivity. However, such experiments are essential for a precise understanding of fundamental mechanisms and to avoid misinterpretations. Here, we solve this issue by extending 2DES to isolated nanosystems in the gas phase prepared by helium nanodroplet isolation in a molecular beam-type experiment. This approach uniquely provides high flexibility in synthesizing tailored, quantum state-selected model systems of single and many-body character. In a model study of weakly-bound Rb2 and Rb3 molecules we demonstrate the method's unique capacity to elucidate interactions and dynamics in tailored quantum systems, thereby also bridging the gap to experiments in ultracold quantum science.

Phase-synchronous undersampling in nonlinear spectroscopy.

We introduce the concept of phase-synchronous undersampling in nonlinear spectroscopy. The respective theory is presented and validated experimentally in a phase-modulated quantum beat experiment by sampling high phase modulation frequencies with low laser repetition rates. The advantage of undersampling in terms of signal quality and reduced acquisition time is demonstrated, and breakdown conditions are identified. The presented method is particularly beneficial for experimental setups with limited signal/detection rates.

Phase-modulated harmonic light spectroscopy.

By combining phase-modulated nonlinear spectroscopy with second harmonic generation, the concept of phase-modulated harmonic light spectroscopy is introduced. Simultaneous spectroscopy with different harmonics of the light is demonstrated and linear and nonlinear excitation of the spectroscopic sample is investigated. Sum frequency generation and stray light effects during temporal pulse overlap have been evaluated in detail, accompanied by simulations. The presented work provides a promising concept to facilitate coherent nonlinear time-domain spectroscopy in the extreme ultraviolet wavelength regime and contributes valuable insights for future studies in this direction.

Phase-modulated electronic wave packet interferometry reveals high resolution spectra of free Rb atoms and Rb*He molecules.

Phase-modulated wave packet interferometry is combined with mass-resolved photoion detection to investigate rubidium atoms attached to helium nanodroplets in a molecular beam experiment. The spectra of atomic Rb electronic states show a vastly enhanced sensitivity and spectral resolution when compared to conventional pump-probe wave packet interferometry. Furthermore, the formation of Rb*He exciplex molecules is probed and for the first time a fully resolved vibrational spectrum for transitions between the lowest excited 5Π3/2 and the high-lying electronic states 2(2)Π, 4(2)Δ, 6(2)Σ is obtained and compared to theory. The feasibility of applying coherent multidimensional spectroscopy to dilute cold gas phase samples is demonstrated in these experiments.