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High levels of 2-hydroxyisobutyric acid (2-HIBA) were found in urines of patients with obesity and hepatic steatosis, suggesting a potential involvement of this metabolite in clinical conditions. The gut microbial origin of 2-HIBA was hypothesized, however its actual origin and role in biological processes are still not clear. We investigated how treatment with 2-HIBA affected the physiology of the model organism

Ultrafast reactions activated by light absorption are governed by multidimensional excited-state (ES) potential energy surfaces (PESs), which describe how the molecular potential varies with the nuclear coordinates. ES PESs ad-hoc displaced with respect to the ground state can drive subtle structural rearrangements, accompanying molecular biological activity and regulating physical/chemical properties. Such displacements are encoded in the Franck-Condon overlap integrals, which in turn determine the resonant Raman response. Conventional spectroscopic approaches only access their absolute value, and hence cannot determine the sense of ES displacements. Here, we introduce a two-color broadband impulsive Raman experimental scheme, to directly measure complex Raman excitation profiles along desired normal modes. The key to achieve this task is in the signal linear dependence on the Frank-Condon overlaps, brought about by non-degenerate resonant probe and off-resonant pump pulses, which ultimately enables time-domain sensitivity to the phase of the stimulated vibrational coherences. Our results provide the tool to determine the magnitude and the sensed direction of ES displacements, unambiguously relating them to the ground state eigenvectors reference frame.

Intense light-matter interactions and unique structural and electrical properties make Van der Waals heterostructures composed by Graphene (Gr) and monolayer transition metal dichalcogenides (TMD) promising building blocks for tunnelling transistors, flexible electronics, as well as optoelectronic devices, including photodetectors, photovoltaics and quantum light emitting devices (QLEDs), bright and narrow-line emitters using minimal amounts of active absorber material. The performance of such devices is critically ruled by interlayer interactions which are still poorly understood in many respects. Specifically, two classes of coupling mechanisms have been proposed: charge transfer (CT) and energy transfer (ET), but their relative efficiency and the underlying physics is an open question. Here, building on a time resolved Raman scattering experiment, we determine the electronic temperature profile of Gr in response to TMD photo-excitation, tracking the picosecond dynamics of the G and 2D bands. Compelling evidence for a dominant role ET process accomplished within a characteristic time of ~ 4 ps is provided. Our results suggest the existence of an intermediate process between the observed picosecond ET and the generation of a net charge underlying the slower electric signals detected in optoelectronic applications., Comment: 32 pages, 15 figures

Spontaneous Raman microscopy reveals the chemical composition of a sample in a label-free and non-invasive fashion by directly measuring the vibrational spectra of molecules. However, its extremely low cross section prevents its application to fast imaging. Stimulated Raman scattering (SRS) amplifies the signal by several orders of magnitude thanks to the coherent nature of the nonlinear process, thus unlocking high-speed microscopy applications that provide analytical information to elucidate biochemical mechanisms with subcellular resolution. Nevertheless, in its standard implementation, narrowband SRS provides images at only one frequency at a time, which is not sufficient to distinguish constituents with overlapping Raman bands. Here, we report a broadband SRS microscope equipped with a home-built multichannel lock-in amplifier simultaneously measuring the SRS signal at 32 frequencies with integration time down to 44 µs, allowing for detailed, high spatial resolution mapping of spectrally congested samples. We demonstrate the capability of our microscope to differentiate the chemical constituents of heterogeneous samples by measuring the relative concentrations of different fatty acids in cultured hepatocytes at the single lipid droplet level and by differentiating tumor from peritumoral tissue in a preclinical mouse model of fibrosarcoma.

Stimulated Raman scattering (SRS) represents a powerful tool for accessing the vibrational properties of molecular compounds or solid state systems. From a spectroscopic perspective, SRS is able to capture Raman spectra free from incoherent background processes and typically ensures a signal enhancement of several orders of magnitude with respect to its spontaneous counterpart. Since its discovery in 1962, SRS has been applied to develop technological applications, such as Raman-based lasers, frequency shifters for pulsed sources and Raman amplifiers. For the full exploitation of their potential, however, it is crucial to have an accurate description of the SRS processes under the large gain regime. Here, by taking as an example the stimulated Raman spectrum of a model solvent, namely liquid cyclohexane, we discuss how the spectral profiles and the lineshapes of Raman excitations critically depend on the pump excitation regime. In particular, we show that in the large light–matter interaction limit the Raman gain undergoes an exponential increase (decrease) in the red (blue) side of the spectrum, with the Raman linewidths that appear sharpened (broadened).

Spontaneous Raman spectroscopy is a powerful characterization tool for graphene research. Its extension to the coherent regime, despite the large nonlinear third-order susceptibility of graphene, has so far proven challenging. Due to its gapless nature, several interfering electronic and phononic transitions concur to generate its optical response, preventing to retrieve spectral profiles analogous to those of spontaneous Raman. Here we report stimulated Raman spectroscopy of the G-phonon in single and multi-layer graphene, through coherent anti-Stokes Raman Scattering. The nonlinear signal is dominated by a vibrationally non-resonant background, obscuring the Raman lineshape. We demonstrate that the vibrationally resonant coherent anti-Stokes Raman Scattering peak can be measured by reducing the temporal overlap of the laser excitation pulses, suppressing the vibrationally non-resonant background. We model the spectra, taking into account the electronically resonant nature of both. We show how coherent anti-Stokes Raman Scattering can be used for graphene imaging with vibrational sensitivity., Coherent anti-Stokes Raman Scattering (CARS) accesses the vibrational properties of a material via nonlinear four-wave mixing (FWM); CARS in graphene has not been observed to date despite its high nonlinear third-order susceptibility. Here, the authors devised a FWM scheme to perform stimulated Raman spectroscopy in single and multi-layer graphene through CARS.

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

Density fluctuations in simple liquids are analysed in the context of three different and widely used formalisms, whose equivalence in the hydrodynamic limit is shown. We, furthermore, address the issue of the dispersion of the propagating modes outside the hydrodynamics, by comparing three different definitions of the generalized sound velocity. The first definition is standard in statistical mechanics. It relates the sound velocity to the imaginary part of the complex conjugate poles of the so-called intermediate scattering function. Other definitions, frequently used in the literature, identify the characteristic frequencies of the inelastic excitations with the maxima of the inelastic features of the dynamic structure factor, or with the maxima of the current function. The behaviour of these three quantities in the hydrodynamic limit is discussed. Deviations from hydrodynamic dispersion law are also considered with particular emphasis given to the analysis of different sound propagation regimes related to different density fluctuations decay channels.

Coherent artefact is a well-known nonlinear process plaguing ultrafast time-resolved experiments. Here, a Femtosecond-Stimulated-Raman-Scattering based approach, able to disentangle genuine dynamics from coherent artefacts, is introduced for demonstrating optically-driven femtosecond enhancement of the exchange interaction. © 2020 The Author(s)

Excited state vibrations are crucial for determining the photophysical and photochemical properties of molecular compounds. Stimulated Raman scattering can coherently stimulate and probe molecular vibrations with optical pulses, but it is generally restricted to ground state properties. Working under resonance conditions enables cross-section enhancement and selective excitation to a targeted electronic level but is hampered by an increased signal complexity due to the presence of overlapping spectral contributions. Here, we show how detailed information about ground and excited state vibrations can be disentangled by exploiting the relative time delay between Raman and probe pulses to control the excited state population, combined with a diagrammatic formalism to dissect the pathways concurring with the signal generation. The proposed method is then exploited to elucidate the vibrational properties of the ground and excited electronic states in the paradigmatic case of cresyl violet. We anticipate that the presented approach holds the potential for selective mapping of the reaction coordinates pertaining to transient electronic stages implied in photoactive compounds.

Monitoring the interactions between electronic and vibrational degrees of freedom in molecules is critical to our understanding of their structural dynamics. This is typically hampered by the lack of spectroscopic probes able to detect different energy scales with high temporal and frequency resolution. Coherent Raman spectroscopy can combine the capabilities of multidimensional spectroscopy with structural sensitivity at ultrafast timescales. Here, we develop a three-color-based 2D impulsive stimulated Raman technique that can selectively probe vibrational mode couplings between different active sites in molecules by taking advantage of resonance Raman enhancement. Three temporally delayed pulses generate nuclear wave packets whose evolution reports on the underlying potential energy surface, which we decipher using a diagrammatic approach enabling us to assign the origin of the spectroscopic signatures. We benchmark the method by revealing vibronic couplings in the ultrafast dynamics following photoexcitation of the green fluorescent protein.

Electronic properties and lattice vibrations are supposed to be strongly correlated in metal-halide perovskites, due to the "soft" fluctuating nature of their crystal lattice. Thus, unveiling electron-phonon coupling dynamics upon ultra-fast photoexcitation is necessary for understanding the optoelectronic behaviour of the semiconductor. Here, we use impulsive vibrational spectroscopy to reveal ground and excited state vibrational modes of methylammonium lead-bromide perovskite. We observe a coherent phonon at 106 cm-1 (13 meV), pertaining to the inorganic octahedral, which is peculiar of the electronic excited state and generated via displacive excitation mechanism. This indicates the formation of a new geometry, reached after a quarter of the phonon period T/4=80 fs, and fully equilibrated within the phonon lifetime of about 1 ps. Our observations unambiguously prove that this mode drives the crystalline distortion occurring upon carrier generation, implying the presence of polaronic effects., 8 pages, 2 figures

The "Frenkel line" (FL), the thermodynamic locus where the time for a particle to move by its size equals the shortest transverse oscillation period, has been proposed as a boundary between recently discovered liquid-like and gas-like regions in supercritical fluids. We report a simulation study of isothermal supercritical neon in a range of densities intersecting the FL. Specifically, structural properties and single-particle and collective dynamics are scrutinized to unveil the onset of any anomalous behavior at the FL. We find that (i) the pair distribution function smoothly evolves across the FL displaying medium-range order, (ii) low-frequency transverse excitations are observed below the "Frenkel frequency", and (iii) the high-frequency shear modulus does not vanish even for low-density fluids, indicating that positive sound dispersion characterizing the liquid-like region of the supercritical state is unrelated to transverse dynamics. These facts critically undermine the definition of the FL and its significance for any relevant partition of the supercritical phase.

In impulsive stimulated Raman scattering, vibrational oscillations, coherently stimulated by a femtosecond Raman pulse, are monitored in real time and read out as intensity modulations in the transmission of a temporally delayed probe pulse. Critically, in order to retrieve broadband Raman spectra, a fine sampling of the time delays between the Raman and probe pulses is required, making conventional ISRS ineffective for probing irreversible phenomena and/or weak scatterers typically demanding long acquisition times, with signal-to-noise ratios that crucially depend on the pulse fluences and overlap stabilities. To overcome such limitations, here we introduce the chirped-based impulsive stimulated raman scattering (CISRS) technique. Specifically, we show how introducing a chirp in the probe pulse can be exploited for recording the Raman information without the need to scan over the Raman-probe pulse delay. We then experimentally demonstrate with a few examples how to use the introduced scheme to measure Raman spectra.

Author(s): Batignani, G; Pontecorvo, E; Bossini, D; Ferrante, C; Fumero, G; Cerullo, G; Mukamel, S; Scopigno, T | Abstract: Illuminating a magnetic material with femtosecond laser pulses induces complex ultrafast dynamical processes. The resulting optically detectable response usually contains contributions from both the optical properties and the magnetic degrees of freedom. Disentangling all the different components concurring to the generation of the total signal is a major challenge of contemporary experimental solid-state physics. Here, this problem is tackled, addressing the purely optical, nonmagnetic artifacts on the time resolved two-magnon stimulated Raman spectrum of an antiferromagnet, rationalizing the recent observation on the exchange energy modification upon photo-excitation. It is demonstrated how the genuine dynamics of the magnetic eigenmode can be disentangled from the nonlinear optical effects, generated by cross phase modulation, on the femtosecond timescale. The introduced approach can be extended for the investigation of l100nfs dynamic processes by means of coherent Ramannscattering.

Femtosecond stimulated Raman scattering is a time-resolved vibrational spectroscopic technique able to access sub-picosecond dynamics and providing accurate structural information. Thanks to an appropriate combination of three laser pulses, triggering vibrational coherences delayed with respect to the photoinduced event of interest, it is capable of uncompromised temporal precision (down to 50 fs) and spectral resolution (a few wavenumbers), better than spontaneous Raman. Reaching such extreme time scales requires significant temporal overlap of pulses, which gives rise to undesired nonlinear artifacts, often hampering an immediate interpretation of the Raman spectra. Building on a perturbative expansion of the density matrix, we identify the origin of such artifacts in cross phase modulation effects and show how they can be theoretically evaluated and factored out from the signals. We experimentally benchmark the theoretical predictions in a nonreactive model system, namely cyclohexane.

A proposal for building a new Free Electron Laser facility at the Laboratori Nazionali di Frascati, EuPRAXIA@SPARC_LAB, is at present under consideration. This FEL facility will exploit plasma acceleration to produce ultra-bright photon pulses with durations of few femtoseconds down to the wavelengths between 2 and 4 nm, in the so called “water window”. The main class of experiments to be performed will include coherent diffraction imaging, soft X-ray absorption spectroscopy, Raman and photofragmentation measurements. In this article we present the updates on the photon beamlines design for the facility.

In a previous letter and other papers, we have interpreted the supercritical region of fluids as being parted into a gas-like and a liquid-like regimes. The boundary between these two distinct regions of the P-T phase diagram of substances is represented by the Widom line, extending the subcritical liquid-gas 1st order transition line above the critical point. Out authors have been commenting on our interpretation, claiming that the two regions are parted by the so called Frenkel line, which does not reconnect to the subcritical liquid-gas phase boundary. In this work, we show on a solid theoretical basis that the Frenkel line is incorrect and that indeed the Widom line is the relevant boundary between to two supercritical regimes.

© the Owner Societies 2015. We introduce a general theoretical description of non resonant impulsive femtosecond stimulated Raman spectroscopy in a multimode harmonic model. In this technique an ultrashort actinic pulse creates coherences of low frequency modes and is followed by a paired narrowband Raman pulse and a broadband probe pulse. Using closed-time-path-loop (CTPL) diagrams, the response on both the red and the blue sides of the broadband pulse with respect to the narrowband Raman pulse is calculated, the process couples high and low frequency modes, which share the same ground state. The transmitted intensity oscillates between the red and the blue side, while the total number of photons is conserved. The total energy of the probe signal is periodically modulated in time by the coherence created in the low frequency modes.

We introduce a novel configuration for stimulated Raman scattering (SRS) microscopy, called In-line Balanced Detection (IBD), which employs a birefringent plate to generate a time-delayed polarization-multiplexed collinear replica of the probe, acting as a reference. Probe and reference cross the sample at the same position, thus maintaining their balance during image acquisition. IBD can be implemented in any conventional SRS setup, by adding a few simple elements, bringing its sensitivity close to the shot-noise limit even with a noisy laser. We tested IBD with a fiber-format laser system and observed signal-to-noise ratio improvement by up to 30 dB.

The equilibrium optical phonons of graphene are well characterized in terms of anharmonicity and electron–phonon interactions; however, their non-equilibrium properties in the presence of hot charge carriers are still not fully explored. Here we study the Raman spectrum of graphene under ultrafast laser excitation with 3 ps pulses, which trade off between impulsive stimulation and spectral resolution. We localize energy into hot carriers, generating non-equilibrium temperatures in the ~1700–3100 K range, far exceeding that of the phonon bath, while simultaneously detecting the Raman response. The linewidths of both G and 2D peaks show an increase as function of the electronic temperature. We explain this as a result of the Dirac cones’ broadening and electron–phonon scattering in the highly excited transient regime, important for the emerging field of graphene-based photonics and optoelectronics., Non-equilibrium ultrafast processes in graphene entail relaxation pathways involving electron–electron and electron–phonon scattering events. Here, the authors probe graphene optical phonons at high electronic temperatures by means of Raman spectroscopy under pulsed excitation

Photophysical and photochemical processes are often dominated by molecular vibrations in various electronic states. Dissecting the corresponding, often overlapping, spectroscopic signals from different electronic states is a challenge hampering their interpretation. Here we address impulsive stimulated Raman spectroscopy (ISRS), a powerful technique able to coherently stimulate and record Raman-active modes using broadband pulses. Using a quantum-mechanical treatment of the ISRS process, we show the mode-specific way the various spectral components of the broadband probe contribute to the signal generated at a given wavelength. We experimentally demonstrate how to manipulate the signal by varying the probe chirp and the phase-matching across the sample, thereby affecting the relative phase between the various contributions to the signal. These novel control knobs allow us to selectively enhance desired vibrational features and distinguish spectral components arising from different excited states.

Summary form only given. Electron-phonon scattering and anharmonicity are the dominant mechanisms, that enable to describe the equilibrium phonon properties in graphene and Raman scattering is the main tool for their characterization. In the first tens fs after the photoexcitation, an out of equilibrium distribution of (hot) electron is induced with respect to the (cold) phonon bath. Within a few picoseconds, the fast electron-electron and electron-phonon non radiative recombination channels determine the equilibrium between the electronic distribution and the lattice. Therefore, on the laboratory timescale, continuous wave laser sources, commonly used for high resolution spontaneous Raman scattering, examine already equilibrated carrier-phonon distributions. A way to impulsively localize energy into graphene's electronic subsystem is provided by sub picosecond photoexcitation. While the behaviour of hot charge carriers to such ultrafast perturbation has been thoroughly elucidated unraveling the nature of optical phonons under a strongly out of equilibrium regime is a challenge. We perform spontaneous Raman measurements in graphene by using a 3-ps laser excitation, which is revealed to be a good agreement between impulsive stimulation and the necessity of spectral resolution. Furthermore, we show how the Raman response of graphene can be detected in presence of an electronic subsystem temperature largely exceeding that of the phonon bath. We find a peculiar behaviour of the period and lifetime of both G and 2D phonons as function of the carriers' temperature in the range 1700-3100 K, which is strongly suggestive of a smearing out of the Dirac cones. We rationalize such behaviour by accordingly revisiting the traditional theoretical modeling of the electron-phonon coupling in this highly excited transient scenario, which is critical in the emerging field of graphene-based nanophotonic and optoelectronic devices operating at THz rates.

We demonstrate a wavelength-tunable graphene-synchronized all-fiber laser with Yb and Er cavities spanning 1040–1080 and 1535–1560 nm, corresponding to ~2750–3200 cm−1 frequency detuning. We apply the laser to coherent anti-Stokes Raman spectroscopy.

We perform a back-to-back comparison between two nonlinear vibrational imaging techniques: stimulated Raman scattering (SRS) and balanced detection Raman-induced Kerr effect (BD-RIKE). Using a compact fiber-based laser system for generation of pump and Stokes signals, we image polymer beads as well as human hepatocytes under the same experimental conditions. We show that BD-RIKE, despite the slightly lower signal levels, consistently offers an improved signal-to-noise ratio with respect to SRS, resulting in significantly higher image quality. Importantly, we observe that such quality is not affected by the static birefringence of the sample, which makes BD-RIKE a robust and attractive alternative to SRS. We also highlight a unique advantage of the technique, which is its capability to easily access both the real and imaginary parts of the nonlinear susceptibility, thus allowing for vibrational phase imaging. The phase information can be readily obtained from BD-RIKE with minimal experimental effort and provides an additional chemical selectivity channel for coherent Raman microscopy. Copyright © 2014 John Wiley & Sons, Ltd.

Dietary overload of toxic, free metabolic intermediates leads to disrupted insulin signalling and fatty liver disease. However, it was recently reported that this pathway might not be universal: depletion of histone deacetylase (HDAC) enhances insulin sensitivity alongside hepatic lipid accumulation in mice, but the mechanistic role of microscopic lipid structure in this effect remains unclear. Here we study the effect of Entinostat, a synthetic HDAC inhibitor undergoing clinical trials, on hepatic lipid metabolism in the paradigmatic HepaRG liver cell line. Specifically, we statistically quantify lipid droplet morphology at single cell level utilizing label-free microscopy, coherent anti-Stokes Raman scattering, supported by gene expression. We observe Entinostat efficiently rerouting carbohydrates and free-fatty acids into lipid droplets, upregulating lipid coat protein gene Plin4, and relocating droplets nearer to the nucleus. Our results demonstrate the power of Entinostat to promote lipid synthesis and storage, allowing reduced systemic sugar levels and sequestration of toxic metabolites within protected protein-coated droplets, suggesting a potential therapeutic strategy for diseases such as diabetes and metabolic syndrome.

International audience; Determining the initial pathway for ultrafast energy redistribution within biomolecules is a challenge, and haem proteins, for which energy can be deposited locally in the haem moiety using short light pulses, are suitable model systems to address this issue. However, data acquired using existing experimental techniques that fail to combine sufficient structural sensitivity with adequate time resolution have resulted in alternative hypotheses concerning the interplay between energy flow among highly excited vibrational levels and potential concomitant electronic processes. By developing a femtosecond-stimulated Raman set-up, endowed with the necessary tunability to take advantage of different resonance conditions, here we visualize the temporal evolution of energy redistribution over different vibrational modes in myoglobin. We establish that the vibrational energy initially stored in the highly excited Franck–Condon manifold is transferred with different timescales into low- and high-frequency modes, prior to slow dissipation through the protein. These findings demonstrate that a newly proposed mechanism involving the population dynamics of specific vibrational modes settles the controversy on the existence of transient electronic intermediates.

Conjugated organic polymers based on substituted thiophene units are versatile building blocks of many photoactive materials, such as photochromic molecular switches or solar energy conversion devices. Unraveling the different processes underlying their photochemistry, such as the evolution on different electronic states and multidimensional structural relaxation, is a challenge critical to defining their function. Using femtosecond stimulated Raman scattering (FSRS) supported by quantum chemical calculations, we visualize the reaction pathway upon photoexcitation of the model compound 2-methyl-5-phenylthiophene. Specifically, we find that the initial wavepacket dynamics of the reaction coordinates occurs within the first ≈1.5 ps, followed by a ≈10 ps thermalization. Subsequent slow opening of the thiophene ring through a cleavage of the carbon-sulfur bond triggers an intersystem crossing to the triplet excited state. Our work demonstrates how a detailed mapping of the excited-state dynamics can be obtained, combining simultaneous structural sensitivity and ultrafast temporal resolution of FSRS with the chemical information provided by time-dependent density functional theory calculations.

Spontaneous Raman spectroscopy is a formidable tool to probe molecular vibrations. Under electronic resonance conditions, the cross section can be selectively enhanced enabling structural sensitivity to specific chromophores and reaction centers. The addition of an ultrashort, broadband femtosecond pulse to the excitation field allows for coherent stimulation of diverse molecular vibrations. Within such a scheme, vibrational spectra are engraved onto a highly directional field and can be heterodyne detected overwhelming fluorescence and other incoherent signals. At variance with spontaneous resonance Raman, however, interpreting the spectral information is not straightforward, due to the manifold of field interactions concurring to the third order nonlinear response. Taking as an example vibrational spectra of heme proteins excited in the Soret band, we introduce a general approach to extract the stimulated Raman excitation profiles from complex spectral lineshapes. Specifically, by a quantum treatment of the matter through density matrix description of the third order nonlinear polarization, we identify the contributions which generate the Raman bands, by taking into account for the cross section of each process.

Using Femtosecond Stimulated Raman Scattering, we report the observation of sub-picosecond flow of energy locally deposited in a prototype cofactor -the heme of myoglobin- prior to directing heat into the protein moiety.

The pressure dependence of the glass-transition temperature, Tg(P), of the ionic glass-former 2Ca(NO3)2 x 3KNO3, CKN, has been obtained by molecular dynamics (MD) simulations The liquid-glass difference of thermal expansivity, deltaalpha, heat capacity, deltaCp, and isothermal compressibility, deltak, have been calculated as a function of pressure. It has been found that the Ehrenfest relation dTg/dP = TVdeltaalpha/deltaCp predicts the pressure dependence of Tg, but the other Ehrenfest relation, dTg/dP = deltakappa/deltaalpha, does not. Consequently, the Prigogine-Defay ratio, pi = deltaCpdeltakappa/TVdeltaalpha2, is n pi approximately 1.2 at low pressures, but increases 1 order of magnitude at high pressures. The pressure dependence of the Prigogine-Defay ratio is interpreted in light of recent explanations for the finding pi > 1.

We investigated by inelastic X-ray scattering the dynamical properties of molten potassium in a wide range of momentum transfer, Q, from 1 nm(-1) up to the main peak of the structure factor Q approximate to 17 nm(-1). The observed increase of sound velocity in the low Q region (1 < Q < 3 nm(-1)), has been described within a model characterized by two distinct relaxation processes for the collective dynamics. The obtained results are discussed and compared with those from previous neutron scattering experiments. In particular, we associate the speed-up of the sound velocity to the 'instantaneous' disorder of the liquid as opposed to the argument, supported by some neutron scattering studies, of a transition from a liquid to solid like response of the system. (c) 2007 Elsevier B.V. All rights reserved.

Femtosecond stimulated Raman experiments on the antiferromagnetic system KNiF3 are implemented to understand how the exchange interaction — a crucial interaction that rules magnetic phenomena — is influenced by ultrafast optical excitation. Manipulating the macroscopic phases of solids using ultrashort light pulses has resulted in spectacular phenomena, including metal–insulator transitions1,2,3, superconductivity4 and subpicosecond modification of magnetic order5. The development of this research area strongly depends on the understanding and optical control of fundamental interactions in condensed matter, in particular the exchange interaction. However, disentangling the timescales relevant for the contributions of the exchange interaction and spin dynamics to the exchange energy, Eex, is a challenge. Here, we introduce femtosecond stimulated Raman scattering to unravel the ultrafast photo-induced dynamics of magnetic excitations at the edge of the Brillouin zone. We find that femtosecond laser excitation of the antiferromagnet KNiF3 triggers a spectral shift of the two-magnon line, the energy of which is proportional to Eex. By unravelling the photo-induced modification of the two-magnon line frequency from a dominating nonlinear optical effect, we find that Eex is increased by the electromagnetic stimulus.

The theory of elasticity with spatially fluctuating elastic constants (heterogeneous-elasticity theory) is reviewed. It is shown that the vibrational anomalies associated with the boson peak can be qualitatively and quantitatively explained in terms of this theory. Two versions of a mean-field theory for solving the stochastic equation of motion are presented: the coherent-potential approximation (CPA) and the self-consistent Born approximation (SCBA). It is shown that the latter is included in the former in the Gaussian and weak-disorder limit. We are able to discuss and explain cases in which the change of the vibrational spectrum by varying an external parameter can be accounted for by changing the Debye frequency (elastic transformation) and cases in which this is not possible. In the latter case a change in the distribution of the elastic moduli has occurred.

Glasses are out-of-equilibrium systems aging under the crystallization threat. During ordinary glass formation, the atomic diffusion slows down rendering its experimental investigation impractically long, to the extent that a timescale divergence is taken for granted by many. We circumvent here these limitations, taking advantage of a wide family of glasses rapidly obtained by physical vapor deposition directly into the solid state, endowed with different "ages" rivaling those reached by standard cooling and waiting for millennia. Isothermally probing the mechanical response of each of these glasses, we infer a correspondence with viscosity along the equilibrium line, up to exapoise values. We find a dependence of the elastic modulus on the glass age, which, traced back to temperature steepness index of the viscosity, tears down one of the cornerstones of several glass transition theories: the dynamical divergence. Critically, our results suggest that the conventional wisdom picture of a glass ceasing to flow at finite temperature could be wrong., Comment: 4 figures and 1 supplementary figure

Recent progress in theoretical and simulation studies of collective excitations in supercritical fluids is reviewed. We discuss a methodology of fit-free estimation of dispersion of longitudinal and transverse excitations in simple fluids. The issue of vanishing positive sound dispersion--a viscoelastic increase of the speed of sound from adiabatic one to its high-frequency (elastic) value--with reduction of density, as it was observed in inelastic X-ray scattering experiments on supercritical Ar, is discussed from the point of view of finding distinctions in collective dynamics of low--and high-density supercritical fluids. On the basis of several theoretical models within the extended hydrodynamic description of density-density correlations in liquids analytical expressions for positive sound dispersion are obtained and applied for analysis of time correlation functions obtained from molecular dynamics simulations. A location of a crossover from the liquid-like to gas-like types of collective dynamics is discussed based on general findings for spectra of collective excitations in supercritical Ar and soft sphere fluids.

The experimental results relevant for the understanding of the microscopic dynamics in liquid metals are reviewed, with special regards to the ones achieved in the last two decades. Inelastic Neutron Scattering played a major role since the development of neutron facilities in the sixties. The last ten years, however, saw the development of third generation radiation sources, which opened the possibility of performing Inelastic Scattering with X rays, thus disclosing previously unaccessible energy-momentum regions. The purely coherent response of X rays, moreover, combined with the mixed coherent/incoherent response typical of neutron scattering, provides enormous potentialities to disentangle aspects related to the collectivity of motion from the single particle dynamics. If the last twenty years saw major experimental developments, on the theoretical side fresh ideas came up to the side of the most traditional and established theories. Beside the raw experimental results, therefore, we review models and theoretical approaches for the description of microscopic dynamics over different length-scales, from the hydrodynamic region down to the single particle regime, walking the perilous and sometimes uncharted path of the generalized hydrodynamics extension. Approaches peculiar of conductive systems, based on the ionic plasma theory, are also considered, as well as kinetic and mode coupling theory applied to hard sphere systems, which turn out to mimic with remarkable detail the atomic dynamics of liquid metals. Finally, cutting edges issues and open problems, such as the ultimate origin of the anomalous acoustic dispersion or the relevance of transport properties of a conductive systems in ruling the ionic dynamic structure factor are discussed., 53 pages, 41 figures, to appear in "The Review of Modern Physics". Tentatively scheduled for July issue

The idea of the timescale invariance of relaxation processes in liquids (Yulmetyevetal 2001Phys. Rev. E64 057101; 2002JETPLett.76 147) is used to analyse the short-wave collectiv ee xcitation in liquid sodium, as recently measured by means of very-high-energy-resolution inelastic x-ray scattering (Scopigno et al 2002 Phys. Rev. E 65 031205). The dynamic structure factor, S(Q ,ω ), calculated on the basis of this idea is in very good agreement with the experimental data in the wavevector range from 1.5 to 14. 6n m −1 ,w here pronounced collective excitations exist. The frequency dependence of the non∗

Acoustics dynamics of the molecular glass-former indomethacin (IMC) have been investigated by Brillouin light scattering (BLS) at GHz frequencies. Elastic response of the system has been tracked from the melting temperature down to the glass transition through the supercooled liquid. Both the structural arrest and the vibrational dynamics are described by modeling the experimentally determined dynamic structure factor within the framework of the Langevin equation, through a simplified choice of memory function which allows one to determine sound velocity and the acoustic attenuation coefficient as a function of temperature. The density fluctuation spectra in the glassy phase, as probed by BLS, are compared with time-domain results from photoacoustics experiments. The arising scenario is discussed in the context of current literature reporting inelastic X-ray scattering and BLS in platelet geometry. The link between the probed elastic properties and the non-ergodicity factor of the glass phase is finally scrutinized.

Probing the structural rearrangement of a model photochromic molecular switch provides a window on the fundamental dynamics of electrocyclization reactions. Taking advantage of resonance-enhanced femtosecond stimulated Raman scattering (FSRS) with a broadly tunable Raman excitation wavelength, we selectively probe the competing dynamics of both the reactive and nonreactive conformers of a diarylethene (DAE) derivative that are simultaneously present in solution. Measurements that preferentially probe the electrocyclization (ring-closing) reaction of the reactive species reveal an unexpectedly slow nuclear rearrangement, stretching to tens of picoseconds, in striking contrast with the prompt electronic dynamics in the formation of the closed-ring isomer. The different results from transient electronic and vibrational spectroscopies reflect the different aspects of the reaction that are probed by each technique, depending on whether one considers the electronic state of the molecule or the structural rearrangement of the nuclei. Using a different Raman excitation wavelength selectively probes the picosecond-scale intersystem crossing dynamics of the nonreactive conformer, revealing the vibrational spectra of the singlet and triplet excited states for the first time. The present study paves the way to a more complete understanding of the structural mechanisms accompanying the reversible photochromic switching process.

Static and dynamic autocorrelations of charge density, composed of positive point ions and instantaneous distribution of electron density, are studied in liquid Li in a pressure range from ambient to 186 GPa using ab initio molecular dynamics simulations. It is shown analytically that the long-wavelength limit of the charge-charge static structure factor SQQ(k) of liquid metals is proportional to k4. Time-dependent charge-charge correlations in liquid Li at low pressures show identical relaxation as the density-density time correlation functions, in complete agreement with the linear response theory, whereas at extreme pressures we observed different relaxation of the charge and density autocorrelations. The static and dynamic properties of a part of electron density, that corresponds to the nonspherical distribution around ions, are discussed. © 2014 American Physical Society.

The reaction pathway in photoexcited hemeproteins (ligand dissociation, energy redistribution and structural dynamics) has been unraveled by Femtosecond Stimulated Raman Scattering. The possible existence of short living intermediates as opposed to vibrational relaxation is discussed.

Despite that the thermodynamic distinction between a liquid and the corresponding gas ceases to exist at the critical point, it has been recently shown that reminiscence of gaslike and liquidlike behavior can be identified in the supercritical fluid region, encoded in the behavior of hypersonic waves dispersion. By using a combination of molecular dynamics simulations and calculations within the approach of generalized collective modes, we provide an accurate determination of the dispersion of longitudinal and transverse collective excitations in soft-sphere fluids. Specifically, we address the decreasing rigidity upon density reduction along an isothermal line, showing that the positive sound dispersion, an excess of sound velocity over the hydrodynamic limit typical for dense liquids, displays a nonmonotonic density dependence strictly correlated to that of thermal diffusivity and kinematic viscosity. This allows rationalizing recent observation parting the supercritical state based on the Widom line, i.e., the extension of the coexistence line. Remarkably, we show here that the extremals of transport properties such as thermal diffusivity and kinematic viscosity provide a robust definition for the boundary between liquidlike and gaslike regions, even in those systems without a liquid-gas binodal line. Finally, we discuss these findings in comparison with recent results for Lennard-Jones model fluid and with the notion of the "rigid-nonrigid" fluid separation lines.

This paper describes the scientific aims and potentials as well as the preliminary technical design of RUDE, an innovative tool for multi-disciplinary investigations in a wide field of scientific, technological and industrial applications. IRIDE will be a high intensity "particles factory", based on a combination of high duty cycle radio-frequency superconducting electron linacs and of high energy lasers. Conceived to provide unique research possibilities for particle physics, for condensed matter physics, chemistry and material science, for structural biology and industrial applications, IRIDE will open completely new research possibilities and advance our knowledge in many branches of science and technology. [RIDE is also supposed to be realized in subsequent stages of development depending on the assigned priorities. (C) 2013 Elsevier B.V. All rights reserved.

New inelastic X-ray scattering experiments have been performed on liquid lithium in a wide wavevector range. With respect to the previous measurements, the instrumental resolution, improved up to 1.5 meV, allows to accurately investigate the dynamical processes determining the observed shape of the the dynamic structure factor, $S(Q,\omega)$. A detailed analysis of the lineshapes shows the co-existence of relaxation processes with both a slow and a fast characteristic timescales, and therefore that pictures of the relaxation mechanisms based on a simple viscoelastic model must be abandoned., Comment: 5 pages, 4 .PS figures

The sound attenuation in the THz region is studied down to T 16 K in glassy glycerol by inelastic x-ray scattering. At striking variance with the decrease found below 100 K in the GHz data, the attenuation in the THz range does not show any T dependence. This result (i) indicates the presence of two different attenuation mechanisms, active, respectively, in the high- and low-frequency limits, (ii) demonstrates the nondynamic origin of the attenuation of THz sound waves, and confirms a similar conclusion obtained in SiO2 glass by molecular dynamics, and (iii) supports the low-frequency attenuation mechanism proposed by Fabian and Allen [ Phys. Rev. Lett. 82, 1478 (1999)].

We present new inelastic X-ray scattering data for the dynamic structure factor S(Q, ω) of liquid lithium collected at two different temperatures (T = 475K and T = 600K) and in a wide range of exchanged wave-vectors (Q = 1 nm−1 to Q=110nm−1). The analysed Q range covers the transition from collective to single-particle regimes. The spectra have been put on an absolute scale using its first sum rules, and the result obtained has been tested on diffraction data and novel molecular dynamie results. A relaxation fingerprint is observed at low wave-vectors (the so-called positive dispersion of the apparent sound speed), while at higher Q the single particle behaviour gradually emerges.