Real-time measurement and control of particle-number density and size of the detonation products of lead azide

Time-resolved measurement and modeling of the number density and size of lead particles produced following the detonation of Lead Azide (LA) are presented. Particles expanding freely into vacuum through a supersonic nozzle or interacting with a barrier placed above the LA sample are monitored via attenuation of laser beams at 0.67, 1.3 and 10.6 µm. The attenuation depends on the conditions of expansion, but is always much more pronounced at 0.67 µm and 1.3 µm. From the ratio between the attenuations at 0.67 µm and 10.6 µm, the radius and number density of the particles are calculated applying Beer's law and Mie's theory. It is found that 20–90 µs following the detonation the attenuation at 32–36 mm above the LA sample is due to particles with radii of 0.9, 0.7 and 0.1 µm for free expansion into vacuum through the nozzle or near the barrier, respectively. Also, the expansion through the nozzle results in a transparent medium above the nozzle exit for the first few µs following the detonation. The effect of the nozzle is attributed to the fact that the velocity of the expanding detonation products is supersonic, which leads to compression and heating in the throat region, in contrast to the more familiar phenomenon of cooling at subsonic velocities. The dynamics of particles expanding under the different conditions and the mechanism of size reduction and elimination of particles is discussed.     

Rovibrational spectroscopy and intramolecular dynamics of 1,2-trans-d(2)-ethene in the first C-H stretch overtone region

The first overtone region of the C-H stretching vibration of 1,2-trans-d(2)-ethene (HDC=CDH) was monitored via jet-cooled action spectroscopy and room temperature photoacoustic spectroscopy. The spectra include a strong band, which we assigned as the nu(1)+nu(9) C-H stretch vibration, and five additional bands related to transitions to coupled states. The spectral features were modeled in terms of a six-state deperturbation analysis, revealing the energies of the zero-order states and the relatively strong couplings between the initially excited nu(1)+nu(9) state and the doorway states. Considering these energies and the fundamental frequencies of 1,2-trans-d(2)-ethene and presuming that only low-order resonances are involved in the couplings enabled the assignment of the states. The analysis also allowed obtaining insight on energy flow and to find out that the energy oscillations between the C-H stretch state and the doorway states occur on a subpicosecond time scale.     

Vibrationally mediated photodissociation of ethene isotopic variants preexcited to the fourth C-H stretch overtone

H and D photofragments produced via vibrationally mediated photodissociation of jet-cooled normal ethene (C2H4), 1,2-trans-d2-ethene (HDCCDH), and 1,1-d2-ethene (CH2CD2), initially excited to the fourth C-H stretch overtone region, were studied for the first time. H and D vibrational action spectra and Doppler profiles were measured. The action spectra include partially resolved features due to rotational cooling, while the monitored room temperature photoacoustic spectra exhibit only a very broad feature in each species. Simulation of the spectral contours allowed determination of the band types and origins, limited precision rotational constants, and linewidths, providing time scales for energy redistribution. The H and D Doppler profiles correspond to low average translational energies and show slight preferential C-H over C-D bond cleavage in the deuterated variants. The propensities toward H photofragments emerge even though the energy flow out of the initially prepared C-H stretch is on a picosecond time scale and the photodissociation occurs following internal conversion, indicating a more effective release of the light H atoms.     

The I2 dissociation mechanisms in the chemical oxygen-iodine laser revisited

The recently suggested mechanism of I(2) dissociation in the chemical oxygen-iodine laser (COIL) [K. Waichman, B. D. Barmashenko, and S. Rosenwaks, J. Appl. Phys. 106, 063108 (2009); and J. Chem. Phys. 133, 084301 (2010)] was largely based on the suggestion of V. N. Azyazov, S. Yu. Pichugin, and M. C. Heaven [J. Chem. Phys. 130, 104306 (2009)] that the vibrational population of O(2)(a) produced in the chemical generator is high enough to play an essential role in the dissociation. The results of model calculations based on this mechanism agreed very well with measurements of the small signal gain g, I(2) dissociation fraction F, and temperature T in the COIL. This mechanism is here revisited, following the recent experiments of M. V. Zagidullin [Quantum Electron. 40, 794 (2010)] where the observed low population of O(2)(b, v = 1) led to the conclusion that the vibrational population of O(2)(a) at the outlet of the generator is close to thermal equilibrium value. This value corresponds to a very small probability, ～0.05, of O(2)(a) energy pooling to the states O(2)(X,a,b, v > 0). We show that the dissociation mechanism can reproduce the experimentally observed values of g, F, and T in the COIL only if most of the energy released in the processes of O(2)(a) energy pooling and O(2)(b) quenching by H(2)O ends up as vibrational energy of the products, O(2)(X,a,b), where the vibrational states v = 2 and 3 are significantly populated. We discuss possible reasons for the differences in the suggested vibrational population and explain how these differences can be reconciled.     

Experiment and modeling of a small-scale,supersonic chemical oxygen-iodine laser

We report on detailed experiment and modeling of a small-scale, supersonic chemical oxygen-iodine laser. The laser has a 5 cm long active medium and utilizes a simple sparger-type O₂(¹ ) chemical generator and a medium-size pumping system. A grid nozzle is used for iodine injection and supersonic expansion. 25 W of cw laser emission at 1.315 µm are obtained in the present experiments. The small size and the simple structure of the laser system and its stable operation for long times make it a convenient tool for studying parameters important for high-power supersonic iodine lasers and for comparison to model calculations. The lasing power is studied as a function of the molar flow rates of the various reagents, and conditions are found for optimal operation. Good agreement is found between the experimental results and calculations based on a simple one-dimensional semi-empirical model, previously developed in our laboratory and modified in the present work. The model is used to predict optimal values for parameters affecting the laser performance that are difficult to examine in the present experimental system.     

Highly sensitive standoff detection of explosives via backward coherent anti-Stokes Raman scattering

The detection of particles of explosives and related compounds by coherent anti-Stokes Raman scattering (B-CARS) was studied in detail. The B-CARS signal intensity was compared to that of spontaneous Raman scattering and its dependence on the distance between the sample and the detection system was found. Our measurements imply that B-CARS allows favorable detection as compared to Raman. It is estimated that for pulse energies of 10 mJ of the pump and Stokes laser beams, detection of trace amounts of samples from distances of ～10 to 200 m might be possible applying B-CARS, depending on the species.     

Mode-dependent enhancement of photodissociation and photoionization in a seven atom molecule

We report the first experimental demonstration of vibrational mode-dependent enhancement in photodissociation and photoionization of a seven atom molecule, methylamine (CH(3)NH(2)). The fundamental C-H stretches and the overtones or combinations of CH(3) bends were prepared via stimulated Raman excitation (SRE) prior to their 243.135 nm one-photon dissociation or two-photon ionization. The photodissociation or photoionization of the vibrationally excited molecules was achieved via 10 ns delayed or temporally overlapping SRE and UV pulses, respectively. It is shown that bending modes are more effective than stretches in promoting photodissociation and photoionization, since their UV excitation is favored by larger Franck Condon factors. This behavior provides clear evidence for vibrational mode-dependence in a relatively large molecule with a torsional degree of freedom, indicating that these modes survive intramolecular vibrational redistribution on a time scale considerably longer than hitherto inferred from previous studies.     

Electronic properties of doped molecular thin films measured by Kelvin probe force microscopy

We report on high-resolution electronic measurements of doped organic thin-film transistors using Kelvin probe force microscopy. Measurements conducted on field effect transistors made of N,NI-diphenyl-N,NI-bis(1-naphthyl)-1,1I-biphenyl-4,4I-diamine p-doped with tetrafluoro-tetracyanoquinodimethane have allowed us to determine the rich structure of the doping-induced density of states. In addition, the doping process changes only slightly the Fermi energy position with respect to the highest occupied molecular orbital level center. The moderate change is explained by two counter-acting effects on the Fermi energy position: the doping-induced additional charge and the broadening of the density of states.     

Production of the n2 herman infrared system by the energy pooling reaction of N2(Δ3Σ+u) metastable nitrogen molecules

Molecular N₂ emission, observed from an Ar(³Po, 2) and Xe(³P₂) + N₂ flowing afterglow apparatus, indicates that the energy pooling reaction by 2N₂(A ³Σ⁺_u) generates the emission from the Herman infrared system, which is an unassigned nitrogen band system. A lower limit to the formation rate constant for the upper state of the Herman infrared system was found to be 2.5 × 10^-11 cm³ molecule^?1 s^?1. The information presented here may help in the identification of the upper and lower states of the emission system. The 2N₂(A) energy pooling reaction also forms N₂(B³ Π_g, v? 8) but a rate constant cannot be assigned from the present data.