Coherent anti-Stokes Raman spectroscopy of single and multi-layer graphene.

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.

Tracking the Connection between Disorder and Energy Landscape in Glasses Using Geologically Hyperaged Amber.

Fossil amber offers the unique opportunity to investigate an amorphous material that has been exploring its energy landscape for more than 110 million years of natural aging. By applying different X-ray scattering methods to amber before and after annealing the sample to erase its thermal history, we identify a link between the potential energy landscape and the structural and vibrational properties of glasses. We find that hyperaging induces a depletion of the vibrational density of states in the terahertz region, also ruling the sound dispersion and attenuation properties of the corresponding acoustic waves. Critically, this is accompanied by a densification with structural implications different in nature from that caused by hydrostatic compression. Our results, rationalized within the framework of fluctuating elasticity theory, reveal how upon approaching the bottom of the potential energy landscape (9% decrease in the fictive temperature) the elastic matrix becomes increasingly less disordered (6%) and longer-range correlated (22%).

Raman spectroscopy of graphene under ultrafast laser excitation.

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.

Behavior of Supercritical Fluids across the "Frenkel Line".

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.

Direct observation of subpicosecond vibrational dynamics in photoexcited myoglobin.

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.

Electronic resonances in broadband stimulated Raman spectroscopy.

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.

Pressure-induced emergence of unusually high-frequency transverse excitations in a liquid alkali metal: Evidence of two types of collective excitations contributing to the transverse dynamics at high pressures.

Unlike phonons in crystals, the collective excitations in liquids cannot be treated as propagation of harmonic displacements of atoms around stable local energy minima. The viscoelasticity of liquids, reflected in transition from the adiabatic to elastic high-frequency speed of sound and in absence of the long-wavelength transverse excitations, results in dispersions of longitudinal (L) and transverse (T) collective excitations essentially different from the typical phonon ones. Practically, nothing is known about the effect of high pressure on the dispersion of collective excitations in liquids, which causes strong changes in liquid structure. Here dispersions of L and T collective excitations in liquid Li in the range of pressures up to 186 GPa were studied by ab initio simulations. Two methodologies for dispersion calculations were used: direct estimation from the peak positions of the L/T current spectral functions and simulation-based calculations of wavenumber-dependent collective eigenmodes. It is found that at ambient pressure, the longitudinal and transverse dynamics are well separated, while at high pressures, the transverse current spectral functions, density of vibrational states, and dispersions of collective excitations yield evidence of two types of propagating modes that contribute strongly to transverse dynamics. Emergence of the unusually high-frequency transverse modes gives evidence of the breakdown of a regular viscoelastic theory of transverse dynamics, which is based on coupling of a single transverse propagating mode with shear relaxation. The explanation of the observed high-frequency shift above the viscoelastic value is given by the presence of another branch of collective excitations. With the pressure increasing, coupling between the two types of collective excitations is rationalized within a proposed extended viscoelastic model of transverse dynamics.

Energy flow between spectral components in 2D broadband stimulated Raman spectroscopy.

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.

Acoustic dynamics of supercooled indomethacin probed by Brillouin light scattering.

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.

Acoustic-like dynamics of amorphous drugs in the THz regime.

The high frequency dynamics of Indomethacin and Celecoxib glasses has been investigated by inelastic x-ray scattering, accessing a momentum-energy region still unexplored in amorphous pharmaceuticals. We find evidence of phonon-like acoustic dynamics, and determine the THz behavior of sound velocity and acoustic attenuation. Connections with ordinary sound propagation are discussed, along with the relation between fast and slow degrees of freedom as represented by non-ergodicity factor and kinetic fragility, respectively.

Acoustic dynamics of network-forming glasses at mesoscopic wavelengths.

The lack of long-range structural order in amorphous solids induces well known thermodynamic anomalies, which are the manifestation of distinct peculiarities in the vibrational spectrum. Although the impact of such anomalies vanishes in the long wavelength, elastic continuum limit, it dominates at length scales comparable to interatomic distances, implying an intermediate transition regime still poorly understood. Here we report a study of such mesoscopic domains by means of a broadband version of picosecond photo-acoustics, developed to coherently generate and detect hypersonic sound waves in the sub-THz region with unprecedented sampling efficiency. We identify a temperature-dependent fractal v(3/2) frequency behaviour of the sound attenuation, pointing to the presence of marginally stable regions and a transition between the two above mentioned limits. The essential features of this behaviour are captured by a theoretical approach based on random spatial variation of the shear modulus, including anharmonic interactions.

Spectrally tailored narrowband pulses for femtosecond stimulated Raman spectroscopy in the range 330-750 nm.

Spectral compression of femtosecond pulses by second harmonic generation in the presence of substantial group velocity dispersion provides a convenient source of narrowband Raman pump pulses for femtosecond stimulated Raman spectroscopy (FSRS). We discuss here a simple and efficient modification that dramatically increases the versatility of the second harmonic spectral compression technique. Adding a spectral filter following second harmonic generation produces narrowband pulses with a superior temporal profile. This simple modification i) increases the Raman gain for a given pulse energy, ii) improves the spectral resolution, iii) suppresses coherent oscillations associated with slowly dephasing vibrations, and iv) extends the useful tunable range to at least 330-750 nm.

Dynamics and Thermodynamics beyond the critical point.

Sudden changes in the dynamical properties of a supercritical fluid model have been found as a function of pressure and temperature (T/T(c) = 2-5 and P/P(c) = 10-10(3)), striving with the notion of a single phase beyond the critical point established by thermodynamics. The sound propagation in the Terahertz frequency region reveals a sharp dynamic crossover between the gas like and the liquid like regimes along several isotherms, which involves, at sufficiently low densities, the interplay between purely acoustic waves and heat waves. Such a crossover allows one to determine a dynamic line in the phase diagram which exhibits a very tight correlation with a number of thermodynamic observables, showing that the supercritical state is remarkably more complex than thought so far.

Vibrational dynamics and surface structure of amorphous selenium.

In contrast to crystalline solids in which structural order governs dynamics and thermodynamics, the lack of long-range periodicity in amorphous materials is responsible for several anomalies. Although the relation between these anomalies and the 'bulk structure' is generally understood, the surface structure and the corresponding vibrational spectrum of amorphous solids is practically an unexplored theme. In this study, we resolve the differences in vibrational dynamics and atomic structure between bulk and surface (top 5 nm) atoms of amorphous selenium. We combine experimental (grazing incidence inelastic X-ray scattering) and computational (ab initio and semiempirical molecular orbital theoretical calculations) methods to scrutinize a variety of possible structural models. We find that a high concentration of particular types of 'coordination defects' in the surface layer is responsible for the observed differences. Resolving the structure of amorphous surfaces is, for example, important for understanding nanoparticles' properties where the surface-to-bulk ratio has a crucial role.

Femtosecond stimulated Raman spectrometer in the 320-520nm range.

Multi-µJ narrow-bandwidth (≈ 10 cm(-1)) picosecond pulses, broadly tunable in the visible-UV range (320-520 nm), are generated by spectral compression of femtosecond pulses emitted by an amplified Ti:sapphire system. Such pulses provide the ideal Raman pump for broadband femtosecond stimulated Raman spectroscopy, as here demonstrated on a heme protein.

High frequency dynamics in liquid nickel: An inelastic x-ray scattering study.

Owing to their large relatively thermal conductivity, peculiar, nonhydrodynamic features are expected to characterize the acousticlike excitations observed in liquid metals. We report here an experimental study of collective modes in molten nickel, a case of exceptional geophysical interest for its relevance in earth interior science. Our result shed light on previously reported contrasting evidences: In the explored energy-momentum region, no deviation from the generalized hydrodynamic picture describing nonconductive fluids is observed. Implications for high frequency transport properties in metallic fluids are discussed.

Origin of the lambda transition in liquid sulfur.

Developing a novel experimental technique, we applied photon correlation spectroscopy using infrared radiation in liquid sulfur around T(lambda), i.e., in the temperature range where an abrupt increase in viscosity by 4 orders of magnitude is observed upon heating within few degrees. This allowed us - overcoming photoinduced and absorption effects at visible wavelengths - to reveal a chain relaxation process with characteristic time in the millisecond range. These results do rehabilitate the validity of the Maxwell relation in sulfur from an apparent failure, allowing rationalizing of the mechanical and thermodynamic behavior of this system within a viscoelastic scenario.