Search

The interaction of intense light with matter gives rise to competing nonlinear responses that can dynamically change material properties. Prominent examples are saturable absorption (SA) and two-photon absorption (TPA), which dynamically increase and decrease the transmission of a sample depending on pulse intensity, respectively. The availability of intense soft X-ray pulses from free-electron lasers (FEL) has led to observations of SA and TPA in separate experiments, leaving open questions about the possible interplay between and relative strength of the two phenomena. Here, we systematically study both phenomena in one experiment by exposing graphite films to soft X-ray FEL pulses of varying intensity, with the FEL energy tuned to match carbon 1s to $\pi^*$ or 1s to $\sigma^*$ transitions. It is observed for lower intensities that the nonlinear contribution to the absorption is dominated by SA attributed to ground-state depletion; for larger intensities ($>10^{14}$ W/cm$^2$), TPA becomes more dominant. The relative strengths of the two phenomena depend in turn on the specific transition driven by the X-ray pulse. Both observations are consistent with our real-time electronic structure calculations. Our results reveal the competing contributions of distinct nonlinear material responses to spectroscopic signals measured in the X-ray regime, demonstrating an approach of general utility for interpreting FEL spectroscopies.

The possibility to obtain a three-dimensional representation of a single object with sub-$\mu$m resolution is crucial in many fields, from material science to clinical diagnostics. This is typically achieved through tomography, which combines multiple two-dimensional images of the same object captured at different orientations. However, this serial imaging method prevents single-shot acquisition in imaging experiments at free electron lasers. In the present experiment, we report on a new approach to 3D imaging using extreme-ultraviolet radiation. In this method, two EUV pulses hit simultaneously an isolated 3D object from different sides, generating independent coherent diffraction patterns, resulting in two distinct bidimensional views obtained via phase retrieval. These views are then used to obtain a 3D reconstruction using a ray tracing algorithm. This EUV stereoscopic imaging approach, similar to the natural process of binocular vision, provides sub-$\mu$m spatial resolution and single shot capability. Moreover, ultrafast time resolution and spectroscopy can be readily implemented, a further extension to X-ray wavelengths can be envisioned as well., Comment: Authors Danny Fainozzi and Matteo Ippoliti contributed equally

The identification of the hydrological processes taking place at coastal systems and the interaction between aquifers and the sea have been key features for many groundwater-related studies. However, the suitability of different boundary conditions for representing the hydrodynamic conditions along the coast in modelling applications is widely discussed today. In this study, a groundwater flow model is developed for a coastal multilayer semi-arid aquifer system (Lavrio, Greece), which in turn is used for the comparison between alternative boundary conditions that are considered relevant for representing the coast. The sensitivity analysis and parameter estimation of the model parameters were conducted using a statistical approach, and the results show that the head-dependent boundary condition can produce a more representative simulation of the coastal system hydrodynamics. The response of the karstic aquifer is also simulated satisfactorily, proving that the modelling code is also suitable for simulating karstic aquifers, at least at a large scale. Finally, the hydraulic interconnection between the different aquifer layers within the study area is clarified, as groundwater is primarily discharged from the karstic to the alluvial aquifer.

We utilize coherent femtosecond extreme ultraviolet (EUV) pulses derived from a free electron laser (FEL) to generate transient periodic magnetization patterns with periods as short as 44 nm. Combining spatially periodic excitation with resonant probing at the dichroic M-edge of cobalt allows us to create and probe transient gratings of electronic and magnetic excitations in a CoGd alloy. In a demagnetized sample, we observe an electronic excitation with 50 fs rise time close to the FEL pulse duration and ~0.5 ps decay time within the range for the electron-phonon relaxation in metals. When the experiment is performed on a sample magnetized to saturation in an external field, we observe a magnetization grating, which appears on a sub-picosecond time scale as the sample is demagnetized at the maxima of the EUV intensity and then decays on the time scale of tens of picoseconds via thermal diffusion. The described approach opens prospects for studying dynamics of ultrafast magnetic phenomena on nanometer length scales.

Expanding the activity of wide bandgap semiconductors from the UV into the visible range has become a central goal for their application in green solar photocatalysis. The hybrid plasmonic/semiconductor system, based on silver nanoparticles (Ag NPs) embedded in a film of CeO2, is an example of a functional material developed with this aim. In this work, we take advantage of the chemical sensitivity of free electron laser (FEL) time-resolved soft X-ray absorption spectroscopy (TRXAS) to investigate the electron transfer process from the Ag NPs to the CeO2 film generated by the NPs plasmonic resonance photoexcitation. Ultrafast changes (

Dimensionality plays a key role in the emergence of ordered phases, such as charge density-waves (CDW), which can couple to, and modulate, the topological properties of matter. In this work, we study the out-of-equilibrium dynamics of the paradigmatic quasi-one-dimensional material (TaSe

An increasing reliance on groundwater resources has been observed worldwide during the past 50–70 years and has led to unsustainable groundwater abstraction in many regions, especially in semi-arid and arid alluvial groundwater basins. Managed aquifer recharge (MAR) has been promoted to replenish overdrafted groundwater basins and augment surface water supply. However, MAR feasibility in alluvial groundwater basins is complicated by complex geologic architecture that typically includes laterally continuous, fine-texture confining units that can impede both recharge rates and regional propagation of increases in the hydraulic head. A greater feasibility of MAR hinges on identifying locations where rapid, high-volume recharge that provides regional increases in pressure head are possible, but relatively little research has evaluated the factors that control MAR feasibility in alluvial groundwater basins. Here, we combine a transition probability Markov chain geostatistical model of the subsurface geologic heterogeneity of the eastern side of the northern Central Valley, California, with the three-dimensional, variably saturated water flow code ParFlow to explore the variability of MAR feasibility in this region. We use a combination of computationally efficient local- and global-sensitivity analyses to evaluate the relative importance of factors that contribute to MAR feasibility. A novel proxy parameter approach was used to describe the configuration and proportions of subsurface hydrofacies and the water table depth for sensitivity analyses, and results suggest that recharge potential is relatively more sensitive to the variability of this proxy parameter than to the variability of individual hydrofacies hydraulic properties. Results demonstrate that large variability of MAR feasibility is typical for alluvial aquifer systems and that outsized recharge rates are possible in select locations where interconnected, coarse-texture hydrofacies occur.

Ultrafast control of magnetization on the nanometer length scale, in particular all-optical switching, is key to putting ultrafast magnetism on the path towards future technological application in data storage technology. However, magnetization manipulation with light on this length scale is challenging due to the wavelength limitations of optical radiation. Here, we excite transient magnetic gratings in a GdFe alloy with a periodicity of 87 nm by interference of two coherent femtosecond light pulses in the extreme ultraviolet spectral range at the free electron laser facility FERMI. The subsequent ultrafast evolution of the magnetization pattern is probed by diffraction of a third, time-delayed pulse tuned to the Gd N-edge at a wavelength of 8.3 nm. By examining the simultaneously recorded first and second diffraction orders and by performing reference real-space measurements with a wide-field magneto-optical microscope with femtosecond time resolution, we can conclusively demonstrate the ultrafast emergence of all-optical switching on the nanometer length scale., 6 pages, 5 figures

In this work, we study the out-of-equilibrium dynamics of the paradigmatic quasi-one-dimensional material (TaSe$_4$)$_2$I, that exhibits a transition into an incommensurate CDW phase when cooled just below room temperature, namely at T$_{\rm{CDW}} $= 263 K. We make use of both optical laser and free-electron laser (FEL) based time-resolved spectroscopies in order to study the effect of a selective excitation on the normal-state and on the CDW phases, by probing the near-infrared/visible optical properties both along and perpendicularly to the direction of the CDW, where the system is metallic and insulating, respectively. Excitation of the core-levels by ultrashort X-ray FEL pulses at 47 eV and 119 eV induces reflectivity transients resembling those recorded when only exciting the valence band of the compound - by near-infrared pulses at 1.55 eV - in the case of the insulating sub-system. Conversely, the metallic sub-system displays a relaxation dynamics which depends on the energy of photo-excitation. Moreover, excitation of the CDW amplitude mode is recorded only for excitation at low-photon-energy. This fact suggests that the coupling of light to ordered states of matter can predominantly be achieved when directly injecting delocalized carriers in the valence band, rather than localized excitations in the core levels. On a complementary side, table-top experiments allow us to prove the quasi-unidirectional nature of the CDW phase in (TaSe$_4$)$_2$I, whose fingerprints are detected along its $c$-axis only. Our results provide new insights on the symmetry of the ordered phase of (TaSe$_4$)$_2$I perturbed by a selective excitation, and suggest a novel approach based on complementary table-top and FEL spectroscopies for the study of complex materials., Comment: 24 pages, 7 figures

Urban groundwater management requires complex environmental models to represent interactions between hydrogeological processes and infrastructure systems. While the impacts of external uncertainties, such as climate and population growth, have been widely studied, there is limited understanding of how decision support is altered by endogenous uncertainties arising from model parameters and observations used for calibration. This study investigates (1) the importance of observation choice and parameter values on aquifer management objectives when controlling for model error and (2) how the relative performance of management alternatives varies when exposed to endogenous uncertainties, both individually and in combination. We use a spatially distributed groundwater model of the Valley of Mexico, where aquifer management alternatives include demand management, targeted infiltration, and wastewater reuse. The effects of uncertainty are evaluated using global sensitivity analysis, performance ranking of alternatives under a range of human–natural parameters, and identification of behavioral parameter sets filtered with an error metric calculated from varying subsets of observations. Results show that the parameters governing hydraulic conductivity and total water use in the basin have the greatest effect on management objectives. Error metrics (i.e., squared residuals of piezometric head) are not necessarily controlled by the same parameters as the head-based objectives needed for decision-making. Additionally, observational and parameter uncertainty each play a larger role in objective variation than the management alternatives themselves. Finally, coupled endogenous uncertainties have amplifying effects on decision-making, leading to larger variations in the ranking of management alternatives than each on their own. This study highlights how the uncertain parameters of a physically based model and their interactions with uncertain observations can affect water supply planning decisions in densely populated urban areas.

Charge transport processes at interfaces play a crucial role in many processes. Here, the first soft x-ray second harmonic generation (SXR SHG) interfacial spectrum of a buried interface (boron-Parylene N) is reported. SXR SHG shows distinct spectral features that are not observed in x-ray absorption spectra, demonstrating its extraordinary interfacial sensitivity. Comparison to electronic structure calculations indicates a boron-organic separation distance of 1.9Å, with changes of less than 1Å resulting in easily detectable SXR SHG spectral shifts (ca. hundreds of milli-electron volts).

The advent of extreme ultraviolet (EUV) and soft x-ray free electron lasers (FELs) has enabled nonlinear optical experiments at wavelengths shorter than the visible-UV range. An important class of experiments is those based on the four-wave-mixing (FWM) approach, which are often based on interactions between pulses at different wavelengths. The exploitation of multiple EUV/soft x-ray wavelengths is not straightforward, but it can significantly expand the range of applications. In this manuscript we report on an experimental approach, based on the concomitant use of a non-collinear split-delay-and-recombination unit (“mini-Timer”) and on a two-color seeded FEL emission scheme (“twin-seed mode”). We used a diamond sample for demonstrating the capability of this setup of generating and detecting a FWM signal stimulated by two-color EUV FEL pulses. This approach can be further exploited for developing experimental methods based on non-linear EUV/x-ray optics.

Understanding and controlling the thermal transport at nanoscale is a key ingredient for the development of future nanoelectronical devices. In this study of thin silicon carbide (SiC) membrane we demonstrate the potential of free electron laser extreme ultraviolet (EUV) transient grating (TG) technique as contactless probe for thermoelastic response at length scales of 84 nm, where the Fourier heat diffusion law is no longer valid. The results have revealed that the mechanical behavior of the system can be fully described in the framework of Lamb waves. Moreover, by use of a bidimensional spatial detector to measure the TG signal, a new feature is the observed, time dependence in the emission angle of the transient diffraction, correlated to the transient grating signal intensity.

Critical groundwater overdraft is one of the greatest water issues of our time. In California, decades of overdraft have resulted in the passage of the 2014 Sustainable Groundwater Management Act, which requires critically overdrafted groundwater basins to create groundwater sustainability plans for future groundwater management. Many managers are using managed aquifer recharge (MAR) in their overall sustainability portfolio, in an attempt to balance groundwater use. Soil maps have been used in the past to determine viability of managed aquifer recharge sites. However, soil maps do not account for the high permeability pathways that exist in the subsurface, which have the potential to provide high efficiency recharge to the water table. This paper emphasizes the utility of creating data dense fine resolution geostatistical models and generating many realizations of the subsurface, which can then be used for analysis to understand the variability in recharge potential for specific recharge sites. These geostatistical realizations were investigated using connectivity metrics to evaluate the spread of highly conductive pathways throughout the subsurface. Connectivity analyses of high conductivity pathways show confidence that the study site- three vineyards located in the floodplain between the Cosumnes River and Deer Creek in Elk Grove, CA - has the potential to provide efficient recharge to the water table. These connectivity analyses can be completed prior to running computationally expensive and time intensive groundwater models and can be used as a way to understand variance between realizations of these geostatistical models.

Self-action nonlinearity is a key aspect -- either as a foundational element or a detrimental factor -- of several optical spectroscopies and photonic devices. Supercontinuum generation, wavelength converters and chirped pulse amplification are just a few examples. The recent advent of Free Electron Lasers (FEL) fostered building on nonlinearity to propose new concepts and extend optical wavelengths paradigms for extreme ultraviolet (EUV) and X-ray regimes. No evidence for intrapulse dynamics, however, has been reported at such short wavelengths, where the light-matter interactions are ruled by the sharp absorption edges of core-electrons. Here, we provide experimental evidence for self-phase modulation of femtosecond FEL pulses, which we exploit for fine self-driven spectral tunability by interaction with sub-micrometric foils of selected monoatomic materials. Moving the pulse wavelength across the absorption edge, the spectral profile changes from a non-linear spectral blue-shift to a red-shifted broadening. These findings are rationalized accounting for ultrafast ionization and delayed thermal response of highly excited electrons above and below threshold, respectively., 20 pages, 6 figures

While climate change will challenge the future of California’s water resources, groundwater can buffer variability in precipitation and streamflow, if managed sustainably. Enhanced river recharge is an important tool to reach sustainable groundwater management in the California Central Valley (USA). Understanding and predicting recharge rates of river water, either natural river bank infiltration or managed aquifer recharge (MAR) during floods (Flood-MAR) or on agricultural land (Ag-MAR) is essential to evaluate the sustainability of groundwater management plans. Groundwater ages, combined with other isotopic and noble gas evidence, can elucidate surface water-groundwater interactions and support river recharge rates calculations over longer time periods.Our study is focused on the recharge from the Cosumnes River in the California Central Valley. The Cosumnes River forms the boundary between the Sacramento Valley groundwater basin to the north and the San Joaquin Valley groundwater basin to the south. For this study, 28 new samples were collected for the analysis of 3H/3He age, noble gases, and stable isotopes. 25 additional samples from the California Waterboards Groundwater Ambient Monitoring and Assessment (GAMA) Shallow Aquifer Assessment program were included, which were collected and analyzed by the USGS California Water Science Center in 2017.We find that 28% of groundwater in the San Joaquin – Cosumnes groundwater subbasin originated as river water recharge, based on the interpolated mean δ18O (7.7 ‰ ), compared with river water (-9 ‰) and local precipitation recharge (-7 ‰) end-members. River water is a source of modern recharge, resulting in high tritium concentrations close to the Cosumnes River. In contrast, ambient groundwater from local precipitation recharge is predominantly pre-modern or fossil, containing less than 1 pCi/L tritium. Combining groundwater ages with the distance to the river, aquifer thickness, and porosity, estimates of river water recharge rate vary between 0.02 km3/yr and 0.035 km3/yr. These quantitative estimates of river water recharge will constrain the numerical groundwater flow model for this basin and aid groundwater managers in developing sustainability plans to balance groundwater pumping with recharge rates.

Expanding the activity of wide bandgap semiconductors from the UV into the visible range has become a central goal for their application in green solar photocatalysis. The hybrid plasmonic/semiconductor system, based on silver nanoparticles (Ag NPs) embedded in a film of CeO2, is an example of a functional material developed with this aim. In this work, we take advantage of the chemical sensitivity of free electron laser (FEL) time-resolved soft X-ray absorption spectroscopy (TRXAS) to investigate the electron transfer process from the Ag NPs to the CeO2 film generated by the NPs plasmonic resonance photoexcitation. Ultrafast changes (

We use femtosecond extreme ultraviolet pulses derived from a free electron laser to excite and probe surface acoustic waves (SAWs) on the (001) surface of single crystal SrTiO3. SAWs are generated by a pair of 39.9 nm pulses crossed at the sample with the crossing angle defining the SAW wavelength at 84 nm. Detection of SAWs is performed via diffraction of a time-delayed 13.3 nm probe pulse by SAW-induced surface ripples. Despite the low reflectivity of the sample in the extreme ultraviolet range, the reflection mode detection is found to be efficient because of an increase in the diffraction efficiency for shorter wavelengths. We describe a methodology for extracting the SAW attenuation in the presence of a thermal grating, which is based on measuring the decay of oscillations at twice the SAW frequency. The proposed approach can be used to study ultrahigh frequency SAWs in a broad range of materials and will bridge the wave vector gap in surface phonon spectroscopy between Brillouin scattering and He atom scattering.

Optical-domain Transient Grating (TG) spectroscopy is a versatile background-free four-wave-mixing technique used to probe vibrational, magnetic and electronic degrees of freedom in the time domain. The newly developed coherent X-ray Free Electron Laser sources allow its extension to the X-ray regime. Xrays offer multiple advantages for TG: their large penetration depth allows probing the bulk properties of materials, their element-specificity can address core-excited states, and their short wavelengths create excitation gratings with unprecedented momentum transfer and spatial resolution. We demonstrate for the first time TG excitation in the hard X-ray range at 7.1 keV. In Bismuth Germanate (BGO), the nonresonant TG excitation generates coherent optical phonons detected as a function of time by diffraction of an optical probe pulse. This experiment demonstrates the ability to probe bulk properties of materials and paves the way for ultrafast coherent four-wave-mixing techniques using X-ray probes and involving nanoscale TG spatial periods., Comment: 11 pages, 4 figures

We present hard x-ray-pump, optical-probe transient grating measurements. A split-and-delay line generates an interference pattern; subsequently an optical probe diffracts from the excited sample. Both the x-ray-x-ray delay and the x-ray-optical delay were varied.

The development of ultra-bright extreme ultraviolet (EUV) and X-ray free electron laser (FEL) sources has enabled the extension of wave-mixing approaches into the short wavelength regime. Such a class of experiments relies upon nonlinear interactions among multiple light pulses offering a unique tool for exploring the dynamics of ultrafast processes and correlations between selected excitations at relevant length and time scales adding elemental and site selectivity as well. Besides the availability of a suitable photon source, the implementation of wave mixing methodology requires efforts in developing the instrumental set-up. We have realized at the FERMI FEL two dedicated set-ups to handle multiple FEL beams with preselected parameters in a non-collinear fashion and control their interaction sequence at the target. These unique apparatuses, combined with the exceptional characteristics of the seeded FERMI FEL, have allowed us to make the first steps into this field and further advances are foreseen in the near future.

Ultrafast time-resolved extreme ultraviolet (EUV) reflectivity measurements of optically pumped amorphous carbon (a-C) have been performed with the FERMI free electron laser (FEL). This work extends the energy range used in previous reflectivity studies and adds polarization dependence. The EUV probe is known to be sensitive to lattice dynamics, since in this range the reflectivity is essentially unaffected by the photo-excited surface plasma. The exploitation of both s- and p-polarized EUV radiation permits variation of the penetration depth of the probe; a significant increase in the characteristic time is observed upon increasing the probing depth (1 vs. 5 ps) due to hydrodynamic expansion and consequent destruction of the excited region, implying that there is only a short window during which the probed region is in the isochoric regime. A weak wavelength dependence of the reflectivity is found, consistent with previous measurements and implying a maximum electronic temperature of 0.8 eV ± 0.4.

A liquid carbon ($l$-C) sample is generated through constant volume heating exposing an amorphous carbon foil to an intense ultrashort laser pulse. Time-resolved x-ray absorption spectroscopy at the C $K$ edge is used to monitor the dynamics of the melting process revealing a subpicosecond rearrangement of the electronic structure associated with a sudden change of the C bonding hybridization. The obtained $l$-C sample, resulting from a nonthermal melting mechanism, reaches a transient equilibrium condition with a temperature of about 14 200 K and pressure in the order of 0.5 Mbar in about 0.3 ps, prior to hydrodynamic expansion. A detailed analysis of the atomic and electronic structure in solid-density $l$-C based on time-resolved x-ray absorption spectroscopy and theoretical simulations is presented. The method can be fruitfully used for extending the experimental investigation of the C phase diagram in a vast unexplored region covering the ${10}^{3}--{10}^{4}\text{ }\text{ }\mathrm{K}$ temperature range with pressures up to 1 Mbar.

Global-scale gradient-based groundwater models are a new endeavor for hydrologists who wish to improve global hydrological models (GHMs). In particular, the integration of such groundwater models into GHMs improves the simulation of water flows between surface water and groundwater and of capillary rise and thus evapotranspiration. Currently, these models are not able to simulate water table depth adequately over the entire globe. Unsatisfactory model performance compared to well observations suggests that a higher spatial resolution is required to better represent the high spatial variability of land surface and groundwater elevations. In this study, we use New Zealand as a testbed and analyze the impacts of spatial resolution on the results of global groundwater models. Steady-state hydraulic heads simulated by two versions of the global groundwater model G3 M, at spatial resolutions of 5 arc-minutes (9 km) and 30 arc-seconds (900 m), are compared with observations from the Canterbury region. The output of three other groundwater models with different spatial resolutions is analyzed as well. Considering the spatial distribution of residuals, general patterns of unsatisfactory model performance remain at the higher resolutions, suggesting that an increase in model resolution alone does not fix problems such as the systematic overestimation of hydraulic head. We conclude that (1) a new understanding of how low-resolution global groundwater models can be evaluated is required, and (2) merely increasing the spatial resolution of global-scale groundwater models will not improve the simulation of the global freshwater system.

The conversion of optical and electrical energies in novel materials is key to modern optoelectronic and light-harvesting applications. Here, we investigate the equilibration dynamics of photoexcited 2,7-bis(biphenyl-4-yl)-2′,7′-ditertbutyl-9,9′-spirobifluorene (SP6) molecules adsorbed on ZnO(10-10) using femtosecond time-resolved two-photon photoelectron and optical spectroscopies. We find that, after initial ultrafast relaxation on femtosecond and picosecond time scales, an optically dark state is populated, likely the SP6 triplet (T) state, that undergoes Dexter-type energy transfer ( rDex = 1.3 nm) and exhibits a long decay time of 0.1 s. Because of this long lifetime, a photostationary state with average T–T distances below 2 nm is established at excitation densities in the 1020 cm−2 s−1 range. This large density enables decay by T–T annihilation (TTA) mediating autoionization despite an extremely low TTA rate of kTTA = 4.5 ⋅ 10−26 m3 s−1. The large external quantum efficiency of the autoionization process (up to 15%) and photocurrent densities in the mA cm−2 range offer great potential for light-harvesting applications.

We demonstrate an all-optical approach for measuring spectrograms of individual FEL pulses by measuring a spectrally-resolved EUV-EUV-optical four-wave-mixing signal. We experimentally demonstrate that this is phase-sensitive can be applied to structured and unstable pulse trains.