Shawn McGrane

Single shot measurements of laser driven shock waves using ultrafast dynamic ellipsometry

Ultrafast dynamic ellipsometry, a diagnostic that measures both the shock-induced optical effects and the motion of shocked materials, has been implemented in a single shot form. This is accomplished using chirped pulse interferometry and probing the sample at two angles with both s- and p-polarized light. The application of single shot ultrafast dynamic ellipsometry should prove important in future studies of shocked transparent materials and metals because it allows concurrent determination of the initial and shocked optical constants, shock and particle velocities, and the picosecond time dependence of these properties with a higher signal-to-noise ratio and less stringent sample requirements than multishot methods. The ability to infer both the initial and shocked refractive indices of the material eliminates the need for performing extra experiments to calibrate the window, greatly simplifying the analysis and making each shot a self-contained experiment. The implementation of this diagnostic is desc...

The elastic-plastic response of aluminum films to ultrafast laser-generated shocks

We present the free surface response of 2, 5, and 8 μm aluminum films to shocks generated from chirped ultrafast lasers. We find two distinct steps to the measured free surface velocity that indicate a separation of the faster elastic wave from the slower plastic wave. We resolve the separation of the two waves to times as short as 20 ps. We measured peak elastic free surface velocities as high as 1.4 km/s corresponding to elastic stresses of 12 GPa. The elastic waves rapidly decay with increasing sample thickness. The magnitude of both the elastic wave and the plastic wave and the temporal separation between them was strongly dependent on the incident laser drive energy.We present the free surface response of 2, 5, and 8 μm aluminum films to shocks generated from chirped ultrafast lasers. We find two distinct steps to the measured free surface velocity that indicate a separation of the faster elastic wave from the slower plastic wave. We resolve the separation of the two waves to times as short as 20 ps. We measured peak elastic free surface velocities as high as 1.4 km/s corresponding to elastic stresses of 12 GPa. The elastic waves rapidly decay with increasing sample thickness. The magnitude of both the elastic wave and the plastic wave and the temporal separation between them was strongly dependent on the incident laser drive energy.

Spectrally modified chirped pulse generation of sustained shock waves

A method is described for generating shock waves with 10–20 ps risetime followed by >200 ps constant pressure, using spectrally modified (clipped) chirped laser pulses. The degree of spectral clipping alters the chirped pulse temporal intensity profile and thereby the time-dependent pressure (tunable via pulse energy) generated in bare and nitrocellulose-coated Al thin films. The method is implementable in common chirped amplified lasers, and allows synchronous probing with a <200 fs pulse.

Comparative infrared and Raman spectroscopy of energetic polymers

Infrared and Raman spectra of three energetic polymers, nitrocellulose, glycidyl azide polymer (GAP), and polyvinyl nitrate (PVN), are presented and compared. The bands are assigned to predominant characteristic motions by comparison to similar materials and the literature. The Raman spectra of PVN and GAP, even with 785 nm excitation, are partially obscured by native fluorescence. The inhomogeneous broadening evident in these spectra has implications for use of these energetic polymers in ultrafast spectroscopic studies of shock-induced chemistry.

Control of cis-stilbene photochemistry using shaped ultraviolet pulses.

We demonstrate product branching control of the photoisomerization and cyclization reactions of cis-stilbene dissolved in n-hexane. An acousto-optical modulator-based pulse shaper was used at 266 nm, in a shaped pump-supercontinuum probe technique, to enhance and suppress the relative yields of the cis- to trans-stilbene isomerization as well as the cis-stilbene to 4a,4b-dihydrophenanthrene cyclization. Global, local, and single variable optimization control schemes were all successful at controlling stilbenes excited-state intramolecular rearrangements. The presence of multiphoton transitions was determined to be crucial in changing the yield under the experimental conditions employed. We have mapped experimental conditions in which multiphoton absorption was successful in controlling photoproduct branching ratios in stilbene, illustrated that the intensity dependence of the product yields can provide details of reactive channel branching ratios of higher excited-states, and shown that under the experimental conditions employed (150 fs laser) intensity control was the only mechanism available to the optimal control methods employed that could affect reaction yields.

Sub-picosecond shock interferometry of transparent thin films

Ultrafast spatial interferometric measurements of shock dynamics in transparent thin films exhibit phase shifts caused by both surface motion and the interference of multiple reflections off the moving shock wave interface. The interference effects are strong perturbations on the phase shift, which do not allow independent measurement of surface motion. Calculations of the time dependent phase shift that include reflective surface motion, shock wave transit through the transparent thin film, and thin film interference effects are shown to match experimental measurements in 625-nm-thick films of polymethylmethacrylate (PMMA) shocked to 19 GPa. Interferometric data obtained at two angles of incidence and two polarizations were sufficient to uniquely determine the PMMA shocked refractive index, shock speed, and particle velocity. Interferometric results as a function of shock strength, 2–20 GPa, suggest that submicron PMMA films have essentially the same material response to shock loading (Hugoniot) as macro...

Shock induced chemistry in liquids studied with ultrafast dynamic ellipsometry and visible transient absorption spectroscopy.

The response to ultrafast laser shock loading of nine liquids was monitored in an effort to reveal evidence of chemical changes occurring during the first 350 ps following the shock front. In an effort to compare molecular structures possessing a variety of common bonding patterns, data were acquired for the liquids: cyclohexane, cyclohexene, 1,3-cyclohexadiene, benzene, water, acetonitrile, acrylonitrile, tert-butylacetylene, and phenylacetylene. Transient absorption spectra were measured in the spectral region from 440 to 780 nm over shock stress states from 7 to 20 GPa. Ultrafast dynamic ellipsometry was used to measure the shock and particle velocity as well as the shocked refractive index. Significant transient absorption attributed to chemical reaction was observed for shocked phenylacetylene and acrylonitrile. Evidence of volume decreasing chemical reactions was also observed in the ultrafast dynamic ellipsometry data for phenylacetylene and acrylonitrile. The liquid 1,3-cyclohexadiene exhibited volume decreasing reaction in the ultrafast dynamic ellipsometry data but did not exhibit an increase in the transient absorption spectra. There was no evidence of chemical reaction in cyclohexane, cyclohexene, benzene, water, acetonitrile, or tert-butylacetylene in the first 350 ps, despite the application of shock stress that was in many cases well above the reaction threshold observed at microsecond time scales.

Photoactive high explosives: linear and nonlinear photochemistry of petrin tetrazine chloride.

Pentaerythritol tetranitrate (PETN), a high explosive, initiates with traditional shock and thermal mechanisms. In this study, the tetrazine-substituted derivative of PETN, pentaerythritol trinitrate chlorotetrazine (PetrinTzCl), is being investigated for a photochemical initiation mechanism that could allow control over the chemistry contributing to decomposition leading to initiation. PetrinTzCl exhibits a photochemical quantum yield (QYPC) at 532 nm not evident with PETN. Using static spectroscopic methods, we observe energy absorption on the tetrazine (Tz) ring that results in photodissociation yielding N2, Cl-CN, and Petrin-CN as the major photoproducts. The QYPC was enhanced with increasing irradiation intensity. Experiment and theoretical calculations imply this excitation mechanism follows sequential photon absorption. Dynamic simulations demonstrate that the relaxation mechanism leading to the observed photochemistry in PetrinTzCl is due to vibrational excitation during internal conversion. PetrinTzCls single photon stability and intensity dependence suggest this material could be stable in ambient lighting, yet possible to initiate with short-pulsed lasers.

Quantum Chemistry Studies of Electronically Excited Nitrobenzene, TNA, and TNT

The electronic excitation energies and excited-state potential energy surfaces of nitrobenzene, 2,4,6-trinitroaniline (TNA), and 2,4,6-trinitrotoluene (TNT) are calculated using time-dependent density functional theory and multiconfigurational ab initio methods. We describe the geometrical and energetic character of excited-state minima, reaction coordinates, and nonadiabatic regions in these systems. In addition, the potential energy surfaces for the lowest two singlet (S(0) and S(1)) and lowest two triplet (T(1) and T(2)) electronic states are investigated, with particular emphasis on the S(1) relaxation pathway and the nonadiabatic region leading to radiationless decay of S(1) population. In nitrobenzene, relaxation on S(1) occurs by out-of-plane rotation and pyramidalization of the nitro group. Radiationless decay can take place through a nonadiabatic region, which, at the TD-DFT level, is characterized by near-degeneracy of three electronic states, namely, S(1), S(0), and T(2). Moreover, spin-orbit coupling constants for the S(0)/T(2) and S(1)/T(2) electronic state pairs were calculated to be as high as 60 cm(-1) in this region. Our results suggest that the S(1) population should quench primarily to the T(2) state. This finding is in support of recent experimental results and sheds light on the photochemistry of heavier nitroarenes. In TNT and TNA, the dominant pathway for relaxation on S(1) is through geometric distortions, similar to that found for nitrobenzene, of a single ortho-substituted NO(2). The two singlet and lowest two triplet electronic states are qualitatively similar to those of nitrobenzene along a minimal S(1) energy pathway.

Coherent control of multiple vibrational excitations for optimal detection

While the means to selectively excite a single vibrational mode using ultrafast pulse shaping are well established, the subsequent problem of selectively exciting multiple vibrational modes simultaneously has been largely neglected. The coherent control of multiple vibrational excitations has applications in control of chemistry, chemical detection and molecular vibrational quantum information processing. Using simulations and experiments, we demonstrate that multiple vibrational modes can be selectively excited with the concurrent suppression of multiple interfering modes by orders of magnitude. While the mechanism of selectivity is analogous to that of single mode selectivity, the interferences required to select multiple modes require complicated non-intuitive pulse trains. Additionally, we show that selective detection can be achieved by the optimal pulse shape, even when the nature of the interfering species is varied, suggesting that optimized detection should be practical in real world applications. Experimental measurements of the multiplex coherent anti-Stokes Raman spectra (CARS) and CARS decay times of toluene, acetone, cis-stilbene and nitromethane liquids are reported, along with optimizations attempting to selectively excite nitromethane in a mixture of the four solvents. The experimental implementation exhibits a smaller degree of signal to background enhancement than predicted, which is primarily attributed to the single objective optimization methodology and not to fundamental limitations.