Laser pulses into bullets: tabletop shock experiments.

This article discusses tabletop high-throughput laser experiments on shock waves in solids and liquids, where the more usual laser pump pulse is replaced by a 0.5 mm diameter laser-launched bullet, a thin metal disk called a flyer plate. The hypervelocity flyer (up to 6 km s-1 or Mach 18) can have kinetic energy (∼1 J) to briefly produce extreme conditions of temperature and pressure, thousands of K and tens of GPa (1 GPa = 10 000 bar) in a small volume with a rise time <2 ns. The experiments are performed using a "shock compression microscope", a microscope fitted with the laser flyer launcher plus an optical velocimeter, a high-speed laser interferometer that measures the motion of the flyer plate or the sample material after impact. This makes it possible to generate extreme conditions at the push of a button in an intrinsically safe environment, and probe with any of the diagnostics used in microscope experiments, such as high-speed video, optical emission, nonlinear coherent spectroscopies and so on. The barrier to entering this field is relatively low since many laser laboratories already possess much of the needed instrumentation. A brief introduction to shock waves and instrumentation is presented. Then several examples of recent applications are described, including shocked water, the photophysics of fluorescent molecules under extreme conditions, shocked protein solutions, shocked metal-organic frameworks (MOFs), shocked explosives, chemical catalysis in a shocked liquid, and molecules at shocked interfaces. Since one can shoot a bullet at practically anything, there are many emerging opportunities in chemistry, biophysics, materials science, physics and hypervelocity aerodynamics.

Shock Pressure Dependence of Hot Spots in a Model Plastic-Bonded Explosive.

Shock initiation of plastic-bonded explosives (PBX) begins with the formation of so-called "hot spots", which are energetic reactions localized in regions where the PBX microstructure concentrates the input shock wave energy. We developed a model PBX system to study hot spots which consists of a single crystal of the high explosive HMX (cyclotetramethylene-tetranitramine) embedded in a transparent polyurethane binder (J. Phys Chem. A, 2020, 124, 4646-4653). In the current work we use this model system to study the influence of input shock pressure (12-26 GPa) on hot spot generation using micrometer-resolved high-speed imaging and nanosecond-resolved optical pyrometry. By shocking ∼100 HMX single crystals (HMX-SC), two distinct shock pressure thresholds were observed. The threshold for producing single hot spots in some crystals was 15 GPa. At 23 GPa, hot spot density was sufficiently high to lead to rapid deflagration of the entire HMX-SC. It takes about 25 ns after the shock passes for the hot spots to appear to our visible-light detection apparatus which has a noise floor at about 2000 K. That indicates the shock produces nascent hot spots that undergo a thermal explosion that reaches temperatures >2000 K in 25 ns. The initial hot spot temperature is roughly 3800 K which settles down to 3400 K, the adiabatic flame temperature of HMX. The higher initial temperature is attributed to release of stored interfacial strain energy produced by the shock. An initial estimate for the velocity of the flame front originating at an HMX hot spot is 550 m/s.

In operando measurements of high explosives.

In operando studies of high explosives involve dynamic extreme conditions produced as a shock wave travels through the explosive to produce a detonation. Here, we describe a method to safely produce detonations and dynamic extreme conditions in high explosives and in inert solids and liquids on a tabletop in a high-throughput format. This method uses a shock compression microscope, a microscope with a pulsed laser that can launch a hypervelocity flyer plate along with a velocimeter, an optical pyrometer, and a nanosecond camera that together can measure pressures, densities, and temperatures with high time and space resolution (2 ns and 2 µm). We discuss how a detonation builds up in liquid nitromethane and show that we can produce and study detonations in sample volumes close to the theoretical minimum. We then discuss how a detonation builds up from a shock in a plastic-bonded explosive (PBX) based on HMX (1,3,5,7-Tetranitro-1,3,5,7-tetrazocane), where the initial steps are hotspot formation and deflagration growth in the shocked microstructure. A method is demonstrated where we can measure thermal emission from high-temperature reactions in every HMX crystal in the PBX, with the intent of determining which configurations produce the critical hot spots that grow and ignite the entire PBX.

Mechanochemistry of Metal-Organic Frameworks under Pressure and Shock.

ConspectusMetal-organic framework solids (MOFs) are synthetic nanoporous materials that have drawn intense efforts in synthesis and characterization of chemical properties, most notably for their ability to adsorb liquids and gases. They are constructed as "node-spacer" nanostructured materials: metal centers (ions or clusters) connected by organic linkers (commonly containing carboxylate or imidazolate groups) to form crystalline, extended, often highly nanoporous structures. MOFs exhibit a variety of advantages over conventional porous materials: rationally designed synthesis of desired crystal structures and crystal engineering become feasible; great synthetic versatility and ease of incorporating different chemical functionalities are realized; and the use of lightweight organic linkers allows for ultrahigh surface area and porosity previously not accessible to conventional materials (i.e., zeolites and porous carbon). As a consequence, MOFs show great promise for a rapidly expanding collection of applications such as gas storage, separations, catalysis, sensing, and drug delivery.The mechanochemistry of MOFs and their response to shock waves, which we discuss in this Account, have been only partially explored. Mechanochemistry, the connection between the mechanical and the chemical worlds, has ancient origins. Rubbing sticks together to start a fire is mechanochemistry. Only in the past decade or so, however, has mechanochemistry gained a notable focus in the chemical community. In the following discussion, we present a general introduction to the complex mechanochemical behavior of MOFs both under quasi-static compression and under shock loading created by high-speed impact. During elastic deformation, MOFs undergo reversible structural or phase transitions. Plastic deformation of MOFs can result in mechanochemistry and can permanently modify the crystal structure, the pore dimensions and configuration, and the chemical bonding. The large energies required to induce bond rearrangement during plastic deformation suggest an interesting potential of MOFs for shock wave mitigation applications.MOFs are promising materials for shock energy dissipation because of the high density of nanopores which can absorb shock energy as they collapse. We have recently developed a platform to assess shock wave energy attenuation by MOFs and other powdered materials. It uses a tabletop laser-driven flyer plate to impact MOF samples at velocities of up to 2.0 km/s. The pressure of the shock waves that break out from the MOF sample can be measured by photon Doppler velocimetry. By measuring the shock profiles of MOF layers with different thicknesses, we can determine the shock pressure attenuation by the MOF layer. We have identified the two-wave structure of shocks in MOFs caused by nanopore collapse. Electron micrographs of recovered shocked MOFs show distinct zones in the shocked material corresponding to shock powder compaction, nanopore collapse, and chemical bond destruction.

Observing Hot Spot Formation in Individual Explosive Crystals Under Shock Compression.

The formation of hot spots in dynamically compressed, plastic-bonded explosives is known to be the primary mechanism by which these materials ignite and initiate, but hot spots are small, fleeting, and hard to observe. Using a microscope equipped with laser-launched, miniflyer plates, we have studied hot spots in small grains of cyclotetramethylene-tetranitramine (HMX) embedded in a polyurethane binder, shocked to about 20 GPa. A nanosecond video with 4 µm spatial resolution is used to observe hot spot formation and growth, while nanosecond optical pyrometry measured temperature. Using individual ∼200 µm nominally single crystals of HMX (HMX-SC), we observed hot spots forming preferentially on corners or edges. These hot spots are about 4000 K. When there are multiple hot spots, the flame propagated along crystal edges, and the crystal is mostly combusted after about 300 ns. Using polycrystalline grains (HMX-PC), 6000 K hot spots are created near internal defects or crystal junctions. However, the thermal mass of the material at 6000 K is quite small, so after those hot spots cool down, the HMX combustion is similar to the single crystals. Comparing a HMX-based polymer-bonded explosive (PBX) to the individual polymer-bonded HMX-SC and HMX-PC grains shows that the myriad hot spots in the PBX are hotter than HMX-SC and colder than HMX-PC, but they persist for a longer time in PBX than in the individual grains.

Shock Wave Energy Absorption in Metal-Organic Framework.

Recent investigations into the mechanical properties and mechanochemical reactions of metal-organic frameworks (MOFs) have suggested the potential for energy dissipation by multiple mechanisms. Although the possibility of efficient multifunctional shock dissipation by MOFs was suggested by static high pressure studies, there is little known about MOFs under shock compression. Here, we measure the attenuation of shock wave by the MOF denoted zeolitic-imidazolate framework (ZIF-8) in its desolvated, porous state. We find that shock wave dissipation by ZIF-8 occurred by multiple processes: powder compaction, nanopore-collapse, and chemical bond-breakage. The shock energy absorbance in ZIF-8 is proportional to ZIF-8 thickness, allowing the prediction of the thickness of MOF layer needed to attenuate shock waves to a desired lower energy. Compared with PMMA, often used as a standard, ZIF-8 attenuates 7 times more shock energy per unit mass for impacts at a lower velocity of 0.75 km/s and 2.5 times more at a higher velocity of 1.6 km/s. This research illustrates how to improve the ability to attenuate shock waves for personnel and equipment protection by engineering multifunctionality into the shock wave absorbing armor material.

Ultrafast Proton Transfer in Polymer Blends Triggered by Shock Waves.

We describe ultrafast proton transfer in the ground electronic state triggered by the use of shock waves created by high-speed impacts. The emission of Nile Red (NR), a polarity sensing dye, was used to probe the effects of shock compression in a series of polymers, including polymer Brønsted bases blended with organic acid proton donors. NR undergoes a shock-induced red-shift due to an increase both in density and in polymer polarity. In blends with poly(4-vinylpyridine) (PVP) and phenol, NR showed an excess shock-induced red-shift with a distinct time dependence not present in controls that are incapable of proton transfer. The excess red-shift first appeared with 0.8 km·s-1 impacts. Occurring in ca. 10 ns, this NR red-shift was caused by the formation of an ion pair created by shock-triggered proton transfer from phenol to PVP.

Shock Wave Chemistry in a Metal-Organic Framework.

Metal-organic frameworks (MOFs) have potential applications as energy absorbing materials for shock wave energy mitigation due to their nanoporosity. Here we have examined km/s laser-driven flyer plate impacts on a prototypical MOF, ZIF-8. We observed particle fragmentation and morphological changes in microcrystals of ZIF-8 at lower shock pressures (≈2.5 GPa), and amorphization and structural collapse at higher pressures (≈8 GPa). High-speed emission spectroscopy revealed that 50 ns after flyer plate impacts, an emission pulse was generated by ZIF-8 resulting from chemical bonds that were broken and subsequently reformed. MOFs may prove useful in the dissipation of shock wave energy through large structural changes (free volume collapse and endothermic bond breakage).

Effects of water on low-overpotential CO2 reduction in ionic liquid studied by sum-frequency generation spectroscopy.

We used vibrational sum-frequency generation spectroscopy (SFG) to investigate low-overpotential CO2 reduction on a polycrystalline Ag electrode using room temperature ionic liquid (RTIL), 1-ethyl-3-methylimidazolium tetrafluorborate (EMIM-BF4) electrolyte mixtures with 0.3 mol%, 45 mol% and 77 mol% water. Adding water dramatically increases CO2 reduction efficiency up to 87.5 mol%. We found added water reduces the (negative) threshold potential for CO2 reduction from -1.33 V to -0.9 V. Added water also moved the potentials of the nonresonant (NR) SFG minima and caused the CO Stark shift to increase in concert with the reduction threshold. In previous work (N. García Rey and D. D. Dlott, J. Phys. Chem. C, 2015, 119, 20892-20899), with nearly-dry RTIL electrolyte (0.3 mol% water), we concluded a potential-driven structural transition of RTIL in the double layer controlled CO2 reduction. At lower water concentrations, where CO2 reduction was less efficient, CO product appeared primarily on Ag atop sites. At higher water concentrations where CO2 reduction efficiency was greater, adsorbed CO was observed on multiply-bonded sites, which are likely more efficient catalytic sites.

Emission Lifetimes of a Fluorescent Dye under Shock Compression.

The emission lifetimes of rhodamine 6G (R6G) were measured under shock compression to 9.1 GPa, with the dual intents of better understanding molecular photophysics in extreme environments and assessing the usefulness of fluorescence lifetime microscopy to measure spatially dependent pressure distributions in shocked microstructured media. R6G was studied as free dye dissolved in poly(methyl methacrylate) (PMMA), or dye encapsulated in silica microparticles suspended in PMMA. Thin layers of these materials in impedance-matched geometries were subjected to planar single-stage shocks created by laser-driven flyer plates. A synchronized femtosecond laser excited the dye at selected times relative to flyer plate arrival and the emission lifetimes were measured with a streak camera. Lifetimes decreased when shocks arrived. The lifetime decrease was attributed to a shock-induced enhancement of R6G nonradiative relaxation. At least part of the relaxation involved shock-enhanced intersystem crossing. For free dye in PMMA, the lifetime decrease during the shock was shown to be a linear function of shock pressure from 0 to 9 GPa, with a slope of -0.22 ns·GPa(-1). The linear relationship makes it simple to convert lifetimes into pressures. Lifetime measurements in shocked microenvironments may be better than emission intensity measurements, because lifetimes are sensitive to the surrounding environment, but insensitive to intensity variations associated with the motion and optical properties of a dynamically changing structure.

Picosecond dynamics of hydrogen bond rearrangements during phase separation of a triethylamine and water mixture.

The earliest stages of phase separation in a liquid triethylamine (TEA)-water mixture were observed using a picosecond IR laser pulse to produce a temperature jump and ultrafast Raman spectroscopy. Raman spectral changes in the water OH stretching region showed that the temperature rise induced by IR pulses equilibrated within a few tens of picoseconds. Amplitude changes in the TEA CH-stretching region of difference Raman spectra consisted of an initial faster and a subsequent slower process. The faster process within 100 ps is attributed to hydrogen bond weakening caused by the temperature rise. The slower process attributed to phase separation was observed for several nanoseconds, showing the number of hydrogen bond between TEA and water gradually decreased with time. The kinetics of hydrogen bond scission during phase separation indicated a linear growth of the phase-separated component, as observed previously on the nanosecond time scale, rather than the more usual exponential growth. A peak blueshift was observed in the difference Raman spectra during phase separation. This shift implies that hydrogen bond scission of TEA-water aggregates involving very few water molecules took place in the initial stage of phase separation (up to 2 ns), and then was followed by the breaking of TEA-water pairs surrounded by water molecules. This effect may be a result from spatial inhomogeneities associated with the phase separation process: aggregates or clusters existing naturally in solution even below the lower critical soluble temperature.

Modifying vibrational energy flow in aromatic molecules: effects of ortho substitution.

Ultrafast infrared (IR) Raman spectroscopy was used to measure vibrational energy transfer between nitrobenzene nitro and phenyl groups, in the liquid state at ambient temperature, when ortho substituents (-CH3, -F) were introduced. Quantum chemical calculations were used to assign the vibrations of these molecules to three classes, phenyl, nitro, or global. Combining transient anti-Stokes and Stokes Raman spectra determined the energies of multiple molecular vibrational modes, which were summed to determine the aggregate energies in the phenyl, nitro, or global modes. In a previous study (Pein, B. C.; Sun, Y.; Dlott, D. D., J. Phys. Chem. A 2013, 117, 6066-6072) it was shown that, in nitrobenzene, there was no energy transfer from nitro to phenyl or from nitro to global modes, but there was some transfer from phenyl to nitro and phenyl to global. The ortho substituents activated energy flow from nitro-to-phenyl and nitro-to-global and reduced phenyl-to-nitro flow. The -CH3 substituent entirely shut down the phenyl-to-nitro pathway, presumably by efficiently directing some of the phenyl energy into methyl bending excitations. There is (inefficient) unidirectional vibrational energy flow in nitrobenzene only in the nitro-to-phenyl direction, whereas in o-nitrotoluene, vibrational energy flows only in the nitro-to-phenyl direction.

Unidirectional vibrational energy flow in nitrobenzene.

Experiments were performed on nitrobenzene liquid at ambient temperature to probe vibrational energy flow from the nitro group to the phenyl group and vice versa. The IR pump, Raman probe method was used. Quantum chemical calculations were used to sort the normal modes of nitrobenzene into three categories: phenyl modes, nitro modes, and global modes. IR wavelengths in the 2500-3500 cm(-1) range were found that best produced excitations initially localized on nitro or phenyl. Pulses at 2880 cm(-1) excited a nitro stretch combination band. Pulses at 3080 cm(-1) excited a phenyl C-H stretch plus some nitro stretch. With nitro excitation there was no detectable energy transfer to phenyl. With phenyl excitation there was no direct transfer to nitro, but there was some transfer to global modes such as phenyl-nitro stretching, so some of the vibrational amplitude on phenyl moved onto nitro. Thus energy transfer from nitro to phenyl was absent, but there was weak energy transfer from phenyl to nitro. The experimental methods described here can be used to study vibrational energy flow from one part of a molecule to another, which could assist in the design of molecules for molecular electronics and phononics. The vibrational isolation of the nitro group when attached to a phenyl moiety suggests that strongly nonthermal reaction pathways may play an important role in impact initiation of energetic materials having peripheral nitro groups.

New developments in the physical chemistry of shock compression.

This review discusses new developments in shock compression science with a focus on molecular media. Some basic features of shock and detonation waves, nonlinear excitations that can produce extreme states of high temperature and high pressure, are described. Methods of generating and detecting shock waves are reviewed, especially those using tabletop lasers that can be interfaced with advanced molecular diagnostics. Newer compression methods such as shockless compression and precompression shock that generate states of cold dense molecular matter are discussed. Shock compression creates a metallic form of hydrogen, melts diamond, and makes water a superionic liquid with unique catalytic properties. Our understanding of detonations at the molecular level has improved a great deal as a result of advanced nonequilibrium molecular simulations. Experimental measurements of detailed molecular behavior behind a detonation front might be available soon using femtosecond lasers to produce nanoscale simulated detonation fronts.

Thermo-mechanical behavior measurement of polymer-bonded sugar under shock compression using in-situ time-resolved Raman spectroscopy.

Quantitative information regarding the local behavior of interfaces in an inhomogeneous material during shock loading is limited due to challenges associated with time and spatial resolution. This paper reports the development of a novel method for in-situ measurement of the thermo-mechanical response of polymer bonded sugar composite where measurements are performed during propagagtion of shock wave in sucrose crystal through polydimethylsiloxane binder. The time-resolved measurements were performed with 5 ns resolution providing an estimation on local pressure, temperature, strain rate, and local shock viscosity. The experiments were performed at two different impact velocities to induce shock pressure of 4.26 GPa and 2.22 GPa and strain rate greater than 106/s. The results show the solid to the liquid phase transition of sucrose under shock compression. The results are discussed with the help of fractography analyses of sucrose crystal in order to obtain insights into the underlying heat generation mechanism.

Ethylenediamine Catalyzes Nitromethane Shock-to-Detonation in Two Distinct Ways.

Adding amines to liquid nitromethane (NM) is known to lower the threshold for the shock-to-detonation transition because amines catalyze proton transfer reactions that are the initial steps in the energy release process. We studied NM with 1 wt % ethylenediamine (NM/EDA) with 4 ns input shocks using time and space resolved diagnostics: photon Doppler velocimetry (PDV), optical pyrometry, and nanosecond video imaging. The 4 ns shocks are fast enough to time-resolve the reaction kinetics and the shock-to-detonation transition. We find that it is possible to shock ignite the NM/EDA without producing a detonation, so there is more to amine sensitization of the shock-to-detonation process than simply lowering the barrier to initial reactions. We find that although 1 wt % EDA has little effect on the ambient properties of NM, it dramatically alters the Hugoniot. The shock speed in NM/EDA is reduced, indicating that shocked NM/EDA is significantly more compressible than NM. Higher compressibility is associated with greater adiabatic heating, so EDA both lowers the barrier to proton transfer reactions and increases shock energy absorption. To explain the enhanced compressibility, we propose that shocking NM/EDA produces a reactive flow that has a much higher ionic strength than in NM. The sudden transformation from a molecular liquid to an ionic liquid with stronger intermolecular interactions is responsible for enhanced compressibility and shock heating.

Real-time investigations of Pt(111) surface transformations in sulfuric acid solutions.

We present the first broadband sum-frequency generation (SFG) spectra of adlayers from sulfuric acid solutions on Pt(111) surfaces and reveal surface transformations of (bi)sulfate anions in unprecedented detail. SFG amplitudes, bandwidth, and electrochemical Stark tuning of (bi)sulfate vibrational bands centered at 1250-1290 cm(-1) strongly depend on the applied potential and are correlated with prominent voltammetric features. (Bi)sulfate adlayers on Pt(111) are important model systems for weak, specific adsorption of anions on catalytically active surfaces. Although the existence of surface transformations on Pt(111) in dilute H(2)SO(4) solutions has been established by previous studies, so far they have not been observed with surface vibrational spectroscopy. Our results confirm previous reports of a surface transformation at 0.21 V and provide new information on a second transformation at 0.5 V due to surface hydroxyl formation and rearrangement of the electric double layer.

Ultrafast nonlinear coherent vibrational sum-frequency spectroscopy methods to study thermal conductance of molecules at interfaces.

It is difficult to study molecules at surfaces or interfaces because the total number of molecules is small, and this is especially problematic in studies of interfacial molecular dynamics with high time resolution. Vibrational sum-frequency generation (SFG) spectroscopy, where infrared (IR) and visible pulses are combined at an interface, has emerged as a powerful method to probe interfacial molecular dynamics. The nonlinear coherent nature of SFG helps overcome the sensitivity issues, especially when femtosecond IR pulses are used. With femtosecond pulses, a range of vibrational transitions can be probed simultaneously and high time resolution can be achieved. Ultrafast SFG experiments use three pulses, a pump pulse to generate nonequilibrium conditions with a pair of probe pulses, and two time delay parameters. Mapping SFG intensity as a function of the two time delays creates a two-dimensional surface, where one axis (t(1)) provides information about molecular dynamics driven by the pump pulses, and the other axis (t(2)) about the dynamics of the SFG probing process. We present examples of ultrafast SFG measurements drawn from our studies of heat transport through interfacial molecules that are models for molecular wires in electronic circuits. In these flash-heating experiments, a self-assembled monolayer (SAM) of long-chain molecules adsorbed on a metal surface is subjected to a large amplitude (up to 800 K) temperature jump. Specific vibrational reporter groups on the SAM molecules probed by SFG serve as tiny ultrafast thermometers approximately 1.5 A thick with a approximately 1 ps response time. These SFG thermometers can monitor ultrafast heat transport through the SAM molecules. By varying the lengths of the molecular wires we can tell if the heat is propagating ballistically along the chains, at constant speed, or diffusively. In our analysis of 2D SFG methods, we first describe a simpler situation where the visible probe pulse is effectively infinite in duration. This is the usual way time-resolved SFG measurements are made, and the SFG experiment then becomes a function of a single time delay, the pump-IR probe delay t(1). Unfortunately, in this case the SFG signals have a large contribution from the nonresonant (NR) background generated by the metal surface, which adds a great deal of noise to the data, and the time resolution is limited by the molecule's vibrational dephasing time constant T(2), which is often 1 ps or more. We have recently shown that the NR background can be suppressed using a time delay t(2) between IR and visible probe pulses. In this now 2D SFG method, one would expect that information about the molecular response to the pump pulses would be contained in slices along the t(1) axis, but by simulating the experiment we show that the t(1) and t(2) parameters interact. Changing t(2) to suppress the NR background causes t(1) slices to shift in time. We also show how to improve the time resolution of ultrafast SFG experiments while maintaining NR suppression using femtosecond visible pulses at appropriate t(2) delay values.

Ultrafast condensed-phase emission from energetic composites of teflon and nanoaluminum.

Time and wavelength-resolved spectroscopy was used to monitor optical emission from picosecond flash-heated nanoenergetic materials consisting of 50 nm diameter Al/Al(2)O(3) core-shell nanoparticles in a matrix of Teflon(AF) oxidizer. The Al/Teflon was confined between optical windows to emphasize condensed-phase emission rather than emission from gas-phase reaction products. The Al/Teflon emission is compared to control samples of bare Al nanoparticles or nanoparticles in a nominally inert polybutadiene matrix (Al/PB). In all three materials just two types of emission were observed, a broadband (BB) emission peaked at 320 nm stretching out past 700 nm, and a narrowband (NB) emission with approximately 30 nm wide bands at 310 and 400 nm, coincident with the most intense Al atomic emission lines. The BB emission is attributed to a laser-generated Al plasma and the NB emission to excited-state Al atoms in a dense medium. Compared to Al/PB, the plasma in Al/Teflon emits with higher intensity and longer duration. The Al/Teflon excited-state NB emission was also more intense. The energy release characterizing ignition in Al/Teflon could be monitored via the increased emission intensity of the BB and NB species. We find the ignition process can be described with a global time constant of 100 ps, about twice the approximately 50 ps time constant for the initiation process seen in earlier work (Zamkov, M. A.; Conner, R. W.; Dlott, D. D., J. Phys. Chem. C 2007, 111, 10278), where infrared spectroscopy was used to monitor the disappearance of C-F stretch transitions.

Vibrational energy relaxation of liquid aryl-halides X-C6H5 (X = F, Cl, Br, I).

Anti-Stokes Raman spectroscopy was used to probe vibrational energy dynamics in liquid ambient-temperature aryl-halides, X-Ph (X = F, Cl, Br, I; -Ph = C(6)H(5)), following IR excitation of a 3068 cm(-1) CH-stretching transition. Five ring vibrations and two substituent-dependent vibrations were monitored in each aryl-halide. Overall, the vibrational relaxation (VR) lifetimes in aryl-halides were shorter than those in normal benzene (H-Ph). The aryl-halide CH-stretch lifetimes increased in the order F, Cl, Br, I, ranging from 2.5 to 3.4 ps, compared with 6.2 ps in H-Ph. The aryl-halide energy transfer processes were similar overall with four exceptions. Three of the four exceptions could be explained as a result of faster VR of midrange vibrations (1000-1600 cm(-1)) in the heavier aryl-halides. The fourth appeared to result from a coincidental resonance in chlorobenzene that does not occur in the other aryl-halides. Among the aryl-halides, the decay of CH-stretching excitations (∼3070 cm(-1)) was slower in the heavier species, but the decay of midrange vibrations was faster in the heavier species. This seeming contradiction could be explained if VR depended primarily on the density of states (DOS) of the lower tiers of vibrational excitations. The DOS for the first few (1-4) tiers is similar for all aryl-halides in the CH-stretch region, but DOS increases with increasing halide mass in the midrange region.