Ultrafast dynamics of shock compression of molecular monolayers

Femtosecond laser-driven approximately 1 GPa shock waves are used to compress monolayers of hydrocarbon chains. Vibrational sum-frequency generation spectroscopy probes the orientation of the terminal methyl groups. With an odd number (15) of carbon atoms, shock compression is an elastic process that causes the methyl groups to tilt. With an even number (18) of carbon atoms, shock compression is viscoelastic, creating single and double gauche defects. When the shock unloads, single gauche defects remain while double defects relax in 30 ps to single-defect states with more upright methyl groups.     

Ultrafast high repetition rate absorption spectroscopy of polymer shock compression

A dual-beam transient absorption spectrometer for high repetition rate (80 shocks per second) studies of shock compressed materials is described. The apparatus time response is 100 ps, so the time resolution of the shock compression process is generally limited by the shock transit time across the sample. In turn the sample thickness is limited by the sensitivity of the spectrometer. Using 400 nm thick samples of R640 dye aggregates in \textit{poly} methyl methacrylate (PMMA) and a 4.2 GPa laser-driven shock, transient absorption spectra show a shock induced absorption redshift occurring in 500 ps, considerably longer than the 200 ps shock front transit time (round trip) through the sample. This noninstantaneous shock compression is consistent with the $\sim 300$ ps viscoelastic response of PMMA at 4.2 GPa. Received 30 July 2001 / Accepted 13 March 2002 – Published online 17 June 2002     

Shock waves in molecular solids: ultrafast vibrational spectroscopy of the first nanosecond

A novel technique which uses a microfabricated shock target array assembly is described, where the passage of a shock front through a thin (0.5μm) polycrystalline layer and the subsequent unloading process is monitored in real time with ultrafast coherent Raman spectroscopy. Using a high repetition rate laser shock generation technique, high resolution, coherent Raman spectra are obtained in shocked anthracene and in a high explosive material, NTO, with time resolution of ∼ 50 ps. Spectroscopic measurements are presented which yield the shock pressure (up to 5 GPa), the shock velocity (∼ 4 km/s), the shock front risetime (t _r < 25 ps), and the temperature (∼ 400°C). A brief discussion is presented, how this new technique can be used to determine the Hugoniot, the equation of state, the entropy increase across the shock front, and monitor shock induced chemical reactions in real time. Received 28 October 1996 / Accepted 12 November 1996     

Studies on photoinduced effects in pulse-electrodeposited Ag/Hg-1212/CdSe hetero-nanostructures

Metal/superconductor/semiconductor (Ag/Hg-1212/CdSe) hetero-nanostructures have been fabricated using pulse-electrodeposition technique and are characterized by X-ray diffraction (XRD), full-width at half-maximum (FWHM) and scanning electron microscopy (SEM) studies. The junction capacitance of Ag/Hg-1212, Hg-1212/CdSe and Ag/Hg-1212/CdSe heterojunctions is measured in dark and under laser irradiation at room temperature. The nature of the junction formed and built-in-junction potentials were determined. The increase in carrier concentration across the junction due to photo-irradiation has been observed.     

Effect of laser irradiation of C-V characteristics of electrodeposited Ag/Tl-2223/CdSe hetero-nanostructures

One of the innovative technological directions for the high-temperature superconductors has been persued by fabricating the heteroepitaxial multilayer structures such as superconductor-semiconductor heterostructures. In the present investigation, metal/superconductor/semiconductor (Ag/Tl-2223/CdSe) hetero-nanostructures have successfully been fabricated using dc electrodeposition technique and were characterized by X-ray diffraction (XRD), full-width at half-maximum (FWHM) and scanning electron microscopy (SEM) studies. The measurement of junction capacitance as a function of biasing voltage was used for the estimation of junction built-in-potential (V _D) and to study the charge distribution in a heterojunction. The Mott-Schottky plots were measured for each junction in dark and under the photo-irradiation. The effect of laser irradiation on C-V characteristics of hetero-nanostructure has been studied.     

Hydrogen-bond disruption by vibrational excitations in water

An excitation of the OH-stretch nu(OH) of water has unique disruptive effects on the local hydrogen bonding. The disruption is not an immediate vibrational predissociation, which is frequently the case with hydrogen-bonded clusters, but instead is a delayed disruption caused by a burst of energy from a vibrationally excited water molecule. The disruptive effects are the result of a fragile hydrogen-bonding network subjected to a large amount of vibrational energy released in a short time by the relaxation of nu(OH) stretching and delta(H2O) bending excitations. The energy of a single nu(OH) vibration distributed over one, two, or three (classical) water molecules would be enough to raise the local temperature to 1100, 700, or 570 K, respectively. Our understanding of the properties of the metastable water state having this excess energy in nearby hydrogen bonds, termed H2O*, has emerged as a result of experiments where a femtosecond IR pulse is used to pump nu(OH), which is probed by either Raman or IR spectroscopy. These experiments show that the H2O* spectrum is blue-shifted and narrowed, and the spectrum looks very much like supercritical water at approximately 600 K, which is consistent with the temperature estimates above. The H2O* is created within approximately 400 fs after nu(OH) excitation, and it relaxes with an 0.8 ps lifetime by re-formation of the disrupted hydrogen-bond network. Vibrationally excited H2O* with one quantum of excitation in the stretching mode has the same 0.8 ps lifetime, suggesting it also relaxes by hydrogen-bond re-formation.     

Spatially resolved vibrational energy transfer in molecular monolayers

We have shown that it is possible to input heat to one location of a molecule and simultaneously measure its arrival in real time at two other locations, using an ultrafast flash-thermal conductance technique. A femtosecond laser pulse heats an Au layer to approximately 800 degrees C, while vibrational sum-frequency generation spectroscopy (SFG) monitors heat flow into self-assembled monolayers (SAMs) of organic thiolates. Heat flow into the SAM creates thermally induced disorder, which decreases the coherent SFG signal from the CH-stretching transitions. Recent improvements in the technique are described, including the use of nonresonant background-suppressed SFG. The improved apparatus was characterized using alkanethiolate and benzenethiolate SAMs. In the asymmetric 2-methyl benzenethiolate SAM, SFG can simultaneously monitor CH-stretching transitions of both phenyl and methyl groups. The phenyl response to flash-heating occurs at least as fast as the 1 ps time for the Au surface to heat. The methyl response has a faster portion similar to the phenyl response and a slower portion characterized by an 8 ps time constant. The faster portions are attributed to disordering of the methyl-substituted phenyl rings due to thermal excitation of the Au-S adbonds. The slower portion, seen only in the methyl SFG signal, is attributed to heat flow from the metal surface into the phenyl rings and then to the methyl groups.     

Temperature-dependent vibrational dephasing in molecular crystals: a picosecond cars study of naphthalene

The temperature dependence of picosecond CARS of vibrational excitons in naphthalene is presented. Below ≈40 K relaxation is dominated by spontaneous emission of phonons. Above 40 K high-frequency phonons induce dephasing. The results are consistent with a phonon-promoted energy transfer process.     

Ultrafast dynamics of self-assembled monolayers under shock compression: effects of molecular and substrate structure

Laser-driven approximately 1 GPa shock waves are used to dynamically compress self-assembled monolayers (SAMs) consisting of octadecanethiol (ODT) on Au and Ag, and pentanedecanethiol (PDT) and benzyl mercaptan (BMT) on Au. The SAM response to <4 ps shock loading and approximately 25 ps shock unloading is monitored by vibrational sum-frequency generation spectroscopy (SFG), which is sensitive to the instantaneous tilt angle of the SAM terminal group relative to the surface normal. Arrival of the shock front causes SFG signal loss in all SAMs with a material time constant <3.5 ps. Thermal desorption and shock recovery experiments show that SAMs remain adsorbed on the substrate, so signal loss is attributed to shock tilting of the methyl or phenyl groups to angles near 90 degrees. When the shock unloads, PDT/Au returns elastically to its native structure whereas ODT/Au does not. ODT evidences a complicated viscoelastic response that arises from at least two conformers, one that remains kinetically trapped in a large-tilt-angle conformation for times >250 ps and one that relaxes in approximately 30 ps to a nearly upright conformation. Although the shock responses of PDT/Au, ODT/Ag, and BMT/Au are primarily elastic, a small portion of the molecules, 10-20%, evidence viscoelastic response, either becoming kinetically trapped in large-tilt states or by relaxing in approximately 30 ps back to the native structure. The implications of the observed large-amplitude monolayer dynamics for lubrication under extreme conditions of high strain rates are discussed briefly.