E. Pontecorvo

High-frequency longitudinal and transverse dynamics in water

High-resolution, inelastic x-ray scattering measurements of the dynamic structure factor S (Q,omega) of liquid water have been performed for wave vectors Q between 4 and 30 nm(-1) in distinctly different thermodynamic conditions ( T=263-420 K ; at, or close to, ambient pressure and at P=2 kbar ). In agreement with previous inelastic x-ray and neutron studies, the presence of two inelastic contributions (one dispersing with Q and the other almost nondispersive) is confirmed. The study of their temperature and Q dependence provides strong support for a dynamics of liquid water controlled by the structural relaxation process. A viscoelastic analysis of the Q -dispersing mode, associated with the longitudinal dynamics, reveals that the sound velocity undergoes a complete transition from the adiabatic sound velocity ( c(0) ) (viscous limit) to the infinite-frequency sound velocity ( c(infinity) ) (elastic limit). On decreasing Q , as the transition regime is approached from the elastic side, we observe a decrease of the intensity of the second, weakly dispersing feature, which completely disappears when the viscous regime is reached. These findings unambiguously identify the second excitation to be a signature of the transverse dynamics with a longitudinal symmetry component, which becomes visible in S (Q,omega) as soon as the purely viscous regime is left.

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.

Evidence of anomalous dispersion of the generalized sound velocity in glasses

The dynamic structure factor S(Q,ω), of vitreous silica, has been measured by inelastic x-ray scattering in the exchanged wave-vector (Q) region Q=4-16.5 nm - 1 and up to energies ∞ω= 115 meV in the Stokes side. The unprecedented statistical accuracy in such an extended energy range allows us to accurately determine the longitudinal current spectra and the energies of the vibrational excitations. The simultaneous observation of two excitations in the acoustic region and the persistence of propagating sound waves up to Q values comparable with the (pseudo-)Brillouin-zone edge allow us to observe a positive dispersion in the generalized sound velocity that, around Q5 nm - 1 , varies from 6500 to 9000 m/s; this phenomenon was never experimentally observed in a glass.

Structural rearrangement accompanying the ultrafast electrocyclization reaction of a photochromic molecular switch

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.

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 v3/2 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.

Slow dynamics in an azopolymer molecular layer studied by x-ray photon correlation spectroscopy.

We report the results of x-ray photon correlation spectroscopy (XPCS) experiments on multilayers of a photosensitive azo-polymer which can be softened by photoisomerization. Time correlation functions have been measured at different temperatures and momentum transfers (q) and under different illumination conditions (dark, UV or visible). The correlation functions are well described by the Kohlrausch-Williams-Watts (KWW) form with relaxation times that are proportional to q(-1). The characteristic relaxation times follow the same Vogel-Fulcher-Tammann law describing the bulk viscosity of this polymer. The out-of-equilibrium relaxation dynamics following a UV photoperturbation are accelerated, which is in agreement with a fluidification effect previously measured by rheology. The transient dynamics are characterized by two times correlation function, and dynamical heterogeneity is evidenced by calculating the variance χ of the degree of correlation as a function of ageing time. A clear peak in χ appears at a well defined time τ(C) which scales with q(-1) and with the ageing time, in a similar fashion as previously reported in colloidal suspensions [O. Dauchot, Phys. Rev. Lett. 95, 265701 (2005)]. From an accurate analysis of the correlation functions we could demonstrate a temperature and light dependent cross-over from compressed KWW to simple exponential behavior.

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.

High-frequency transverse dynamics in glasses

The improvement in performance of the inelastic x-ray scattering technique has led to accurate determination of the dynamic structure factors of glassy and liquid glycerol, in the region of exchanged momentum Q = 2–23 nm −1 and in the temperature range 80–570 K. Thanks to the improved statistical accuracy, it has been possible to identify, in the spectra at the lower temperatures, besides the propagating longitudinal mode, a second non-Q-dispersing peak at ¯� T ≈ 8. 5m eV. We int erpret this peak as a signature of the transverse dynamics that, in topologically disordered systems, acquires a longitudinal symmetry component. This assignment is substantiated by the observation that this peak still survives, across the glass transition, in the liquid state, and vanishes when the structural relaxation time τα approaches � −1 T :a be haviour consistent with the condition τα� T � 1r equired for the existence of a nonrelaxational transverse-like dynamics in the liquid state.

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.