The vibrational frequency of the amide I transition of peptides is known to be sensitive to the strength of its hydrogen bonding interactions. In an effort to account for interactions with hydrogen bonding solvents in terms of electrostatics, we study the vibrational dynamics of the amide I coordinate of N-methylacetamide in prototypical polar solvents: D2O, CDCl3, and DMSO-d6. These three solvents have varying hydrogen bonding strengths, and provide three distinct solvent environments for the amide group. The frequency-frequency correlation function, the orientational correlation function, and the vibrational relaxation rate of the amide I vibration in each solvent are retrieved by using three-pulse vibrational photon echoes, two-dimensional infrared spectroscopy, and pump-probe spectroscopy. Direct comparisons are made to molecular dynamics simulations. We find good quantitative agreement between the experimentally retrieved and simulated correlation functions over all time scales when the solute-solvent interactions are determined from the electrostatic potential between the solvent and the atomic sites of the amide group.

Pump-probe time-resolved x-ray diffraction of allowed and nearly forbidden reflections in InSb is used to follow the propagation of a coherent acoustic pulse generated by ultrafast laser-excitation. The surface and bulk components of the strain could be simultaneously measured due to the large x-ray penetration depth. Comparison of the experimental data with dynamical diffraction simulations suggests that the conventional model for impulsively generated strain underestimates the partitioning of energy into coherent modes. 78.47.+p 61.10.-i 63.20.-e The absorption of ultrafast laser pulses in opaque materials generates coherent stress when the pulse length is short compared with time for sound to propagate across an optical penetration depth [1]. The resulting strain field consists of both a surface component, static on time scales where thermal diffusion can be ignored, and a bulk component that propagates at the speed of sound (coherent acoustic phonons). This strain is typically probed by optical methods that are sensitive primarily to the phonon component within the penetration depth of the light [1,2]. However, such methods give little information about the surface component of the strain, and, moreover, they are unable to give a quantitative measure of the strain amplitude.Due to their short wavelengths, long penetration depths, and significant interaction with core electrons, x-rays are a sensitive probe of strain. We note that coherent lattice motion adds sidebands to ordinary Bragg reflection peaks due to x-ray Brillouin scattering if the momentum transfer is large compared to the Darwin width, equivalent to phonons of GHz frequency for strong reflections from perfect crystals. This effect was demonstrated many years ago with acoustoelectrically amplified phonons using a conventional x-ray tube [3].With the recent availability of high brightness short-pulse hard x-ray sources, including third generation synchrotron sources and optical laser based sources [4-6], coherent strain generation and propagation can now be probed by x-ray methods in both the frequency and time domains. Recently, time-resolved diffraction patterns of cw ultrasonically excited crystals were obtained with a synchrotron source [7]. Other experiments have employed picosecond time-resolved x-ray diffraction to study transient lattice dynamics in metals [8], organic films [9], and impulsive strain generation and melting in semiconductors [10][11][12][13][14]. In particular Rose-Petruck et al.[10] demonstrated transient ultrafast strain propagation in GaAs by laser-pump x-ray-probe diffraction. In that experiment, x-rays were diffracted far outside the Bragg peak; however, no oscillations in the diffraction efficiency were detected, and the data were consistent with a unipolar strain pulse. In a similar experiment, Lindenberg et al. [13] detected oscillations in the sidebands for an asymmetrically cut InSb crystal using a streak camera. These oscillations were due to lattice compression and were probed for discrete phonon frequencies i...

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Synchrotrons produce continuous trains of closely spaced X-ray pulses. Application of such sources to the study of atomic-scale motion requires efficient modulation of these beams on timescales ranging from nanoseconds to femtoseconds. However, ultrafast X-ray modulators are not generally available. Here we report efficient subnanosecond coherent switching of synchrotron beams by using acoustic pulses in a crystal to modulate the anomalous low-loss transmission of X-ray pulses. The acoustic excitation transfers energy between two X-ray beams in a time shorter than the synchrotron pulse width of about 100 ps. Gigahertz modulation of the diffracted X-rays is also observed. We report different geometric arrangements, such as a switch based on the collision of two counter-propagating acoustic pulses: this doubles the X-ray modulation frequency, and also provides a means of observing a localized transient strain inside an opaque material. We expect that these techniques could be scaled to produce subpicosecond pulses, through laser-generated coherent optical phonon modulation of X-ray diffraction in crystals. Such ultrafast capabilities have been demonstrated thus far only in laser-generated X-ray sources, or through the use of X-ray streak cameras.

Femtosecond optical pulses are used to generate narrow-band terahertz wave forms via optical rectification in a periodically poled lithium niobate crystal. By cooling the crystal to reduce losses due to phonon absorption, we are able to obtain bandwidths as narrow as 18 GHz at a carrier frequency of 1.8 THz. Temperature-dependent measurements show insignificant bandwidth broadening between 10 and 120 K, although the terahertz power substantially decreases as the temperature increases. Absolute power measurements indicate a conversion efficiency of at least 10−5.