Four wave mixing (FWM) processes, based on third-order non-linear light-matter interactions, can combine ultrafast time resolution with energy and wavevector selectivity, and enables to explore dynamics inaccessible by linear methods. [1][2][3][4][5][6][7] The coherent and multi-wave nature of FWM approach has been crucial in the development of cutting edge technologies, such as silicon photonics, 8 sub-wavelength imaging 9 and quantum communications. 10 All these technologies operate with optical wavelengths, which limit the spatial resolution and do not allow probing excitations with energy in the eV range. The extension to shorter wavelengths, that is the extreme ultraviolet (EUV) and soft-x-ray (SXR) range, will allow to improve the spatial resolution and to expand the excitation energy range, as well as to achieve elemental selectivity by exploiting core resonances. [5][6][7][11][12][13][14] So far FWM applications at these wavelengths have been prevented by the absence of coherent sources of sufficient brightness and suitable experimental setups. Our results show how transient gratings, generated by the interference of coherent EUV pulses delivered by the FERMI free electron laser (FEL), 15 can be used to stimulate FWM processes at sub-optical wavelengths. Furthermore, we have demonstrated the possibility to read the time evolution of the FWM signal, which embodies the dynamics of coherent excitations as molecular vibrations. This result opens the perspective for FWM with nanometer spatial resolution and elemental selectivity,

We report measurements of the sound attenuation coefficient in vitreous silica, for sound waves of wavelength between 50 and 80 nm, performed with the new inelastic UV light scattering technique. These data indicate that in silica glass a crossover between a temperature-dependent (at low frequency) and a temperature-independent (at high frequency) acoustic attenuation mechanism occurs at Q 0:15 nm ÿ1 . The absence of any signature in the static structure factor at this Q value suggests that the observed crossover should be associated with local elastic constant fluctuations. DOI: 10.1103/PhysRevLett.97.035501 PACS numbers: 61.43.Fs, 63.50.+x The sound attenuation in disordered materials and its frequency and wavelength dependence are the result of the interplay between two physical mechanisms: one is due to the anharmonicity of the interparticle interactions, and the other to the structural disorder.The anharmonic attenuation of an acoustic sound wave, identified by its wavelength , frequency , and wave vector Q 2 = , is characterized by a specific, temperature-dependent, relaxation time r [1]. At low frequency (! r < 1) this process dominates the sound absorption through mechanisms such as, e.g., the Akhiezer mechanism [2,3]. Accordingly, the sound attenuation coefficient, as measured by the broadening ÿ of the Brillouin peak in the dynamic structure factor S Q; ! , scales as ! 2 and Q 2 . At high frequency ÿ! r > 1, i.e., Q > Q r 1=v r , where v is the sound velocity, the anharmonic attenuation becomes frequency independent [1][2][3].The sound attenuation associated with topological disorder gives rise to a steeper Q dependence of ÿ Q . If Rayleigh scattering is responsible for this attenuation, ÿ / Q 4 is expected for wavelengths larger than the typical defects size 2 =Q R . For Q > Q R , when the Rayleigh scattering regime is abandoned, one expects that ÿ Q is no longer / Q 4 . Experimentally, for Q larger than 1 nm ÿ1 , all glasses studied so far show ÿ / Q x , with x very close to 2 [4,5].This scenario can be summarized by a three-regime behavior of ÿ Q : (i) at low Q, ÿ Q is determined by anharmonic processes, and ÿ Q / Q 2 up to a first (temperature-dependent) crossover Q r 1=v r ; (ii) an intermediate regime, where the Q dependence of ÿ Q is determined by the system dependent strengths of anharmonicity and structural disorder processes; (iii) a high-Q regime, where ÿ Q is determined by the topological disorder and ÿ Q / Q 2 with a temperature-independent coefficient. This picture is highly debated because it critically depends on the location of Q r and Q R in different glasses. In densified v-SiO 2 , for example, the crossover Q R has been hypothesized to be around 2 nm ÿ1 [6].In the most studied case of vitreous silica, similarly to what happens in many other glasses, both Q r and Q R belong to a Q region which is not directly accessed by traditional scattering probes. In the case of v-SiO 2 , clear evidence is reported for the low-and high-Q quadratic behaviors of ÿ Q , using Brillouin light scat...

Exploring the dynamics of matter driven to extreme non-equilibrium states by an intense ultrashort X-ray pulse is becoming reality, thanks to the advent of free-electron laser technology that allows development of different schemes for probing the response at variable time delay with a second pulse. Here we report the generation of two-colour extreme ultraviolet pulses of controlled wavelengths, intensity and timing by seeding of high-gain harmonic generation free-electron laser with multiple independent laser pulses. The potential of this new scheme is demonstrated by the time evolution of a titanium-grating diffraction pattern, tuning the two coherent pulses to the titanium M-resonance and varying their intensities. This reveals that an intense pulse induces abrupt pattern changes on a time scale shorter than hydrodynamic expansion and ablation. This result exemplifies the essential capabilities of the jitter-free multiple-colour free-electron laser pulse sequences to study evolving states of matter with element sensitivity.

Advances in developing ultrafast coherent sources operating at extreme ultraviolet (EUV) and x-ray wavelengths allow the extension of nonlinear optical techniques to shorter wavelengths. Here, we describe EUV transient grating spectroscopy, in which two crossed femtosecond EUV pulses produce spatially periodic nanoscale excitations in the sample and their dynamics is probed via diffraction of a third time-delayed EUV pulse. The use of radiation with wavelengths down to 13.3 nm allowed us to produce transient gratings with periods as short as 28 nm and observe thermal and coherent phonon dynamics in crystalline silicon and amorphous silicon nitride. This approach allows measurements of thermal transport on the ~10-nm scale, where the two samples show different heat transport regimes, and can be applied to study other phenomena showing nontrivial behaviors at the nanoscale, such as structural relaxations in complex liquids and ultrafast magnetic dynamics.

FERMI@Elettra is a free electron-laser (FEL)-based user facility that, after two years of commissioning, started preliminary users' dedicated runs in 2011. At variance with other FEL user facilities, FERMI@Elettra has been designed to deliver improved spectral stability and longitudinal coherence. The adopted scheme, which uses an external laser to initiate the FEL process, has been demonstrated to be capable of generating FEL pulses close to the Fourier transform limit. We report on the first instance of FEL wavelength tuning, both in a narrow and in a large spectral range (fine-and coarse-tuning). We also report on two different experiments that have been performed exploiting such FEL tuning. We used fine-tuning to scan across the 1s-4p resonance in He atoms, at ≈23.74 eV (52.2 nm), detecting both UV-visible fluorescence (4p-2s, 400 nm) and EUV fluorescence (4p-1s, 52.2 nm). We used coarse-tuning to scan the M 4,5 absorption edge of Ge (∼29.5 eV) in the wavelength region 30-60 nm, measured in transmission geometry with a thermopile positioned on the rear side of a Ge thin foil.

We report on the use of the UV Raman technique to monitor the oxidative damage of deoxynucleotide triphosphates (dATP, dGTP, dCTP and dTTP) and DNA (plasmid vector) solutions. Nucleotide and DNA aqueous solutions were exposed to hydrogen peroxide (H2O2) and iron containing carbon nanotubes (CNTs) to produce Fenton's reaction and induce oxidative damage. UV Raman spectroscopy is shown to be maximally efficient to reveal changes in the nitrogenous bases during the oxidative mechanisms occurring on these molecules. The analysis of Raman spectra, supported by numerical computations, revealed that the Fenton's reaction causes an oxidation of the nitrogenous bases in dATP, dGTP and dCTP solutions leading to the production of 2-hydroxyadenine, 8-hydroxyguanine and 5-hydroxycytosine. No thymine change was revealed in the dTTP solution under the same conditions. Compared to single nucleotide solutions, plasmid DNA oxidation has resulted in more radical damage that causes the breaking of the adenine and guanine aromatic rings. Our study demonstrates the advantage of using UV Raman spectroscopy for rapidly monitoring the oxidation changes in DNA aqueous solutions that can be assigned to specific nitrogenous bases.

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The molecular dynamics of water and a polymer matrix is here explored in a paradigmatic model of a polysaccharide hydrogel, by the combined use of UV Raman scattering and infrared measurements. The case example of cyclodextrin nanosponges (CDNS)/hydrogel is chosen since the simultaneous presence in the structure of the polymer matrix of both hydrophilic and hydrophobic sites mimics the complexity of polysaccharide hydrogels. In this way, the contributions provided by the balance between the hydrophilicity/hydrophobicity and the grade of entanglement of the polymer hydrogel to lead to the formation of the gel phase are separately accounted and evaluated. As main results, we found that the hydrophobic CH groups inserted on the aromatic ring of CDNS experience a more pronounced dynamic perturbation with respect to the carbonyl groups due to the collision between the solvent and vibrating atoms of the polymer. The overall results provide a detailed molecular picture of the swelling phenomena occurring when a chemically cross-linked polymer contacts with water or biological fluids and exploits the potentiality of UV Raman spectroscopy to retrieve dynamic information besides their structural counterpart obtained by the classical analysis of the basic features of vibrational spectra.