Search NASA⌕ Search

Engineering topics

Alajajian, S. H.

Publications and source records attributed to Alajajian, S. H..

Negative-ion formation in the explosives RDX, PETN, and TNT using the Reversal Electron Attachment Detection (READ) technique

In the search for high sensitivity and direct atmospheric sampling of trace species, techniques have been developed such as atmospheric-sampling, glow-discharge ionization (ASGDI), corona discharge, atmospheric pressure ionization (API), electron-capture detection (ECD), and negative-ion chemical ionization (NICI) that are capable of detecting parts-per-billion to parts-per-trillion concentrations of trace species. These techniques are based on positive- or negative-ion formation via charge-transfer to the target, or electron capture under multiple-collision conditions in a Maxwellian distribution of electron energies at the source temperature. One drawback of the high-pressure, corona- or glow-discharge devices is that they are susceptible to interferences either through indistinguishable product masses, or through undesired ion-molecule reactions. The ASGDI technique is relatively immune from such interferences, since at target concentrations of less than 1 ppm the majority of negative ions arises via electron capture rather than through ion-molecule chemistry. A drawback of the conventional ECD, and possibly of the ASGDI, is that they exhibit vanishingly small densities of electrons with energies in the range 0-10 millielectron volts (meV), as can be seen from a typical Maxwellian electron energy distribution function at T = 300 K. Slowing the electrons to these subthermal (less than 10 meV) energies is crucial, since the cross section for attachment of several large classes of molecules is known to increase to values larger than 10(exp -12) sq cm at near-zero electron energies. In the limit of zero energy these cross sections are predicted to diverge as epsilon(exp -1/2), where epsilon is the electron energy. In order to provide a better 'match' between the electron energy distribution function and attachment cross section, a new concept of attachment in an electrostatic mirror was developed. In this scheme, electrons are brought to a momentary halt by reversing their direction with electrostatic fields. At this turning point the electrons have zero or near-zero energy. A beam of target molecules is introduced, and the resultant negative ions extracted. This basic idea has been recently improved to allow for better reversal geometry, higher electron currents, lower backgrounds, and increased negative-ion extraction efficiency. We present herein application of the so-called reversal electron attachment detector (READ) to the study of negative-ion formation in the explosives molecules RDX, PETN, and TNT under single-collision conditions.

Chutijian, Ara↗

Negative-ion formation in the explosives RDX, PETN, and TNT by using the reversal electron attachment detection technique

First results of a beam-beam, single-collision study of negative-ion mass spectra produced by attachment of zero-energy electrons to the molecules of the explosives RDX, PETN, and TNT are presented. The technique used is reversal electron attachment detection (READ) wherein the zero-energy electrons are produced by focusing an intense electron beam into a shaped electrostatic field which reverses the trajectory of electrons. The target beam is introduced at the reversal point, and attachment occurs because the electrons have essentially zero longitudinal and radial velocity. The READ technique is used to obtain the 'signature' of molecular ion formation and/or fragmentation for each explosive. Present data are compared with results from atmospheric-pressure ionization and negative-ion chemical ionization methods.

Boumsellek, S.↗

Electron attachment line shapes, cross sections, and rate constants at ultralow energies in CF3SO3H, (CF3SO2)2O, and CF3I

Electron attachment cross sections are reported in the energy range 0-160 meV, and at resolutions of 6.0-6.5 meV (FWHM) for the molecules CF3SO3H (triflic acid), (CF3SO2)2O (triflic anhydride), and CF3I (methyl iodide). Use is made of the Kr photoionization method. Attachment line shapes are deconvoluted from the spectral slit (electron energy) function, and are converted to cross sections by normalization to thermal attachment rate constants at 300 K. Rate constants as a function of mean electron energy are calculated from the cross sections using a Maxwellian electron energy distribution function. Present data are compared with flowing-afterglow, Langmuir-probe results in triflic acid and anhydride, and with high-Rydberg ionization results in CF3I.

Alajajian, S. H.↗

Measurement of threshold temperature effects in dissociative electron attachment to HI and DI

From accurate spectroscopic constants it is found that the thermal dissociative-attachment process (DA) in DI should be exothermic only for rotational levels J greater than 8 in v = O. Here, measurement of an enhancement of DA with rotational temperature T in the range 298-468 K is reported. The effect is easily accounted for by the increase in total fractional population of excited J levels in DI relative to HI. The effect affords a rotational analog to the use of vibrationally excited molecules (e.g., HCl) in a plasma to control electron conduction.

Chutjian, A.↗

Electron attachment lineshapes, cross sections and rate constants at ultra-low energies in several halomethyl and haloethyl molecules

Electron attachment lineshapes, cross sections and rate constants are reported for the molecules CH2Br2, CF2Br2, CF3Br, CBrCl3, BrCN, C2H2Br4, CH3l, C2H5l and 1,1,1,-C2Cl3F3. Use is made of the krypton photoionization method. In addition, the signal intercomparison technique is used to obtain individual channel cross sections and rate constants for Br(-) and CN(-) formation from BrCN, and for Br(-) and Br2(-) formation from CF2Br2. Present results in 1,1,1,-C2Cl3F3 using a new ion extraction grid geometry are compared with earlier results, and differences discussed in terms of the electric field equipotentials of two extraction systems used in the present work. Approximate potential energy curves for BrCN are presented, and the temperature dependence of the Br(-) channel cross section discussed.

Alajajian, S. H.↗

Measurement of electron-attachment line shapes, cross sections, and rate constants in HI and DI at ultralow electron energies

Electron-attachment cross sections are reported in the electron energy range 0-150 MeV, at an energy resolution of 6.5 MeV (full width at half maximum) for the molecules HI and DI. Use is made of the Kr photoionization method to obtain cross sections for HI, and a signal intercomparison technique to obtain cross sections and the thermal-attachment rate constant for DI. Attachment properties of the two molecules are very similar. The ratio of attachment cross sections is discussed in terms of the reduced-mass dependence of the dissociation width and the survival probability, and in terms of spectroscopic thresholds and rotational populations for attachment at 300 K. Approximate potential-energy curves for the lowest states of the neutral molecule and negative ion are given.

Alajajian, S. H.↗

Electron attachment in F2 - Conclusive demonstration of nonresonant, s-wave coupling in the limit of zero electron energy

Dissociative electron attachment to F2 has been observed in the energy range 0-140 meV, at a resolution of 6 meV (full width at half maximum). Results show conclusively a sharp, resolution-limited threshold behavior consistent with an s-wave cross section varying as sq rt of epsilon. Two accurate theoretical calculations predict only p-wave behavior varying as the sq rt of epsilon. Several nonadiabatic coupling effects leading to s-wave behavior are outlined.

Chutjian, A.↗

An intercomparison technique for measuring thermal attachment cross sections and rate constants in distinct final channels

A new technique is introduced for comparing negative-ion signal rates in which a common ion is produced by dissociative attachment in a series of molecules. Measurements are carried out at electron energies less than 100 MeV and at resolutions of 6-8 MeV (FWHM). The technique is demonstrated by detection of the Cl(-) signal in CFCl3, CCl4, CF2Cl2, 1,1,2-C2Cl3F3, 1,1,1-C2Cl3F3 and C2Cl4. Measurements for 1,1,1-C2Cl3F3 show that there is a significant open channel, other than Cl(-) formation, which accounts for about 60 percent of negative-ion formation in thermal-multiple-collision (swarm) experiments. Channel cross sections and rate constants are given for the process Cl(-)/1,1,1-Cl2Cl3F3, as well as in C2Cl4, for the separate channels Cl(-)/C2Cl4 and C2Cl4(-)/C2Cl4.

Alajajian, S. H.↗

Measurements of electron attachment lineshapes and cross sections at ultra-low electron energies for CF2Cl2, c-C4F6, c-C4F8 and c-C7F14

Electron-attachment cross sections are reported in the electron energy range 0-160 meV, and at energy resolutions of 7.0 and 7.5 meV (FWHM), for the molecules CF2Cl2 (dichlorodifluoromethane), c-C4F6 (perfluorocyclobutene), c-C4F8 (perfluorocyclobutane), and c-C7F14 (perfluoromethylcyclohexane). Use is made of the Kr photoionization method. Measured attachment lineshapes are deconvoluted from the spectral slit function, and are converted to cross sections by normalization through thermal attachment-rate constants. Comparisons are made with attachment cross sections derived from several independent sets of swarm-measured rate constants, and with collisional ionization (high-Rydberg attachment) data.

Chutjian, A.↗

Measurements of electron attachment lineshapes and cross sections at ultralow electron energies for c-C6F10, c-C6F12, C8F16 and 1,1,2-C2Cl3F3

Electron attachment cross sections are reported in the electron energy range 0-160 meV and at energy resolutions of 4.5-7.5 meV (FWHM) for the molecules c-C6F10 (perfluorocyclohexene), c-C6F12 (perfluoro-1,2-dimethylcyclobutane), C8F16 (perfluoro-1,3-dimethylcyclohexane) and 1,1,2-C2Cl3F3 (1,1,2-trichlorotrifluoroethane). Use is made of the Kr photoionization technique, and measured attachment lineshapes are converted to cross sections by normalization through attachment rate constants. Comparisons are made with attachment cross sections derived from swarm-measured rate constants. Similar to previous results in eight other molecules, the present four molecules exhibit resolution-limited onsets at a threshold consistent with an s-wave attachment behavior and with a neutral-negative-ion curve crossing at zero energy.

Alajajian, S. H.↗

s-wave threshold in electron attachment - Observations and cross sections in CCl4 and SF6 at ultralow electron energies

The threshold photoionization method was used to study low-energy electron attachment phenomena in and cross sections of CCl4 and SF6 compounds, which have applications in the design of gaseous dielectrics and diffuse discharge opening switches. Measurements were made at electron energies from below threshold to 140 meV at resolutions of 6 and 8 meV. A narrow resolution-limited structure was observed in electron attachment to CCl4 and SF6 at electron energies below 10 meV, which is attributed to the divergence of the attachment cross section in the limit epsilon, l approaches zero. The results are compared with experimental collisional-ionization results, electron-swarm unfolded cross sections, and earlier threshold photoionization data.

Chutjian, A.↗

Reversal ion source - A new source of negative ion beams

A new type of ion source utilizing beams of electrons and target molecules, rather than a diffuse, volume plasma, is described. The source utilizes an electrostatic electron 'mirror' which reverses trajectories in an electron beam, producing electrons at their turning point having a distribution of velocities centered at zero velocity. A gas which attaches zero-velocity electrons is introduced at this turning point. Negative ions are produced by an attachment or dissociative attachment process. For many of the thermal electron-attaching molecules the cross sections can be quite large, varying as the inverse square root of the electron energy or just the s-wave threshold law. The efficiency and current density of the ion source for production of Cl(-) through the large, thermal energy attachment process is estimated. It is argued that the source can be used for the production of negative ions through attachment resonances located at higher energies as well.

Orient, O. J.↗

s-wave threshold in electron attachment - Results in 2-C4F6 and CFCl3 at ultra-low electron energies

Electron attachment lineshapes and cross sections are reported for the processes 2-C4F6(-)/2-C4F6 and Cl(-)/CFCl3 at electron energies of 0-120 and 0-140 meV, and at resolutions of 6 and 7 meV (FWHM), respectively. As in previous measurements in CCl4 and SF6, the results show resolution-limited narrow structure in the cross section at electron energies below 15 meV. This structure arises from the divergence of the s-wave cross section in the limit of zero electron energy. Comparisons are given with swarm-measured results, and with collisional ionization (high-Rydberg attachment) data in this energy range.

Chutjian, A.↗