Application of microwave diagnostics to copper chloride and carbon dioxide lasers

Part A

A problem restricting the development of the CuCl laser has been the decrease in output power with increases of tube temperature above 400°C. At that temperature the CuCl vapor pressure is about .1 torr. This is a small fraction of the buffer gas pressure (He at 10 torr).

The aim of the project was to measure the peak radiation temperature (assumed related to the mean energy of electrons) in the laser discharge as a function of the tube temperature. A 24 gHz gated microwave radiometer was used.

It was found that at the tube temperatures at which the output power began to deteriorate, the electron radiation temperature showed a sharp increase (compared with radiation temperature in pure buffer).

Using the above result, we have postulated that this sudden increase is a result of Penning ionization of the Cu atoms. As a consequence of this process the number of Cu atoms available for lasing decrease.

PART B

The aim of the project was to study the dissociation of CO₂ in the glow discharge of flowing CO₂ lasers.

A TM₀₁₁ microwave (3 gHz) cavity was used to measure the radially averaged electron density n_e and the electron-neutral collision frequency in the laser discharge. An estimate of the electric field is made from these two measurements. A gas chromatograph was used to measure the chemical composition of the gases after going through the discharge. This instrument was checked against a mass spectrometer for accuracy and sensitivity.

Several typical laser mixtures were .used: CO₂-N₂-He (1,3,16), (1,3,0), (1,0,16), (1,2,10), (1,2,0), (1,0,10), (2,3,15), (2,3,0), (2,0,15), (1,3,16)+ H₂O and pure CO₂. Results show that for the conditions studied the dissociation as a function of the electron density is uniquely determined by the STP partial flow rate of CO₂, regardless of the amount of N₂ and/or He present. The presence of water vapor in the discharge decreased the degree of dissociation.

A simple theoretical model was developed using thermodynamic equilibrium. The electrons were replaced in the calculations by a distributed heat source.

The results are analyzed with a simple kinetic model.

Stopping power of gases for heavy ions

Pulse-height and time-of-flight methods have been used to measure the electronic stopping cross sections for projectiles of ¹²C, ¹⁶O, ¹⁹F, ²³Na, ²⁴Mg, and ²⁷Al, slowing in helium, neon, argon, krypton, and xenon. The ion energies were in the range 185 keV ≤ E ≤ 2560 keV.

A semiempirical calculation of the electronic stopping cross section for projectiles with atomic numbers between 6 and 13 passing through the inert gases has been performed using a modification of the Firsov model. Using Hartree-Slater-Fock orbitals, and summing over the losses for the individual charge states of the projectiles, good agreement has been obtained with the experimental data. The main features of the stopping cross section seen in the data, such as the Z₁ oscillation and the variation of the velocity dependence on Z₁ and Z₂, are present in the calculation. The inclusion of a modified form of the Bethe-Bloch formula as an additional term allows the increase of the velocity dependence for projectile velocities above v_o to be reproduced in the calculation.

The separation of atomic and molecular gases from helium by cataphoresis

The cataphoretic purification of helium was investigated for binary mixtures of He with Ar, Ne, N₂, O₂, CO, and CO₂ in DC glow discharge. An experimental technique was developed to continuously measure the composition in the anode end-bulb without sample withdrawal. Discharge currents ranged from 10 ma to 100 ma. Total gas pressure ranged from 2 torr to 9 torr. Initial compositions of the minority component in He ranged from 1.2 mole percent to 7.5 mole percent.

The cataphoretic separation of Ar and Ne from He was found to be in agreement with previous investigators. The cataphoretic separation of N₂, O₂, and CO from He was found to be similar to noble gas systems in that the steady-state separation improved with (1) increasing discharge current, (2) increasing gas pressure, and (3) decreasing initial composition of the minority component. In the He-CO₂ mixture, the CO₂ dissociated to CO plus O₂. The fraction of CO₂ dissociated was directly proportional to the current and pressure and independent of initial composition.

The experimental results for the separation of Ar, Ne, N₂, O₂, and CO from He were interpreted in the framework of a recently proposed theoretical model involving an electrostatic Peclet number. In the model the electric field was assumed to be constant. This assumption was checked experimentally and the maximum variation in electric field was 35% in time and 30% in position. Consequently, the assumption of constant electric field introduced no more than 55% variation in the electrostatic Peclet number during a separation.

To aid in the design of new cataphoretic systems, the following design criteria were developed and tested in detail: (1) electric field independent of discharge current, (2) electric field directly proportional to total pressure, (3) ion fraction of impurity directly proportional to discharge current, and (4) ion fraction of impurity independent of total pressure. Although these assumptions are approximate, they enabled the steady-state concentration profile to be predicted to within 25% for 75% of the data. The theoretical model was also tested with respect to the characteristic time associated with transient cataphoresis. Over 80% of the data was within a factor of two of the calculated characteristic times.

The electrostatic Peclet number ranged in value from 0.13 to 4.33. Back-calculated ion fractions of the impurity component ranged in value from 4.8x10^-6 to 178x10^-6.

Part I. Electric birefringence studies of deoxyribonucleic acids. Part II. Selective dissociation of nucleohistone complexes

Part I

The electric birefringence of dilute DNA solutions has been studied in considerable detail and on a large number of samples, but no new and reliable information was discovered concerning the tertiary structure of DNA. The large number of variables which effect the birefringence results is discussed and suggestions are made for further work on the subject.

The DNA molecules have been aligned in a rapidly alternating (10 to 20 kc/sec) square wave field confirming that the orientation mechanism is that of counterion polarization. A simple empirical relation between the steady state birefringence, Δn_st, and the square of the electric field, E, has been found: Δn_st = E²/(a E² + b), where a = 1/Δn_s and b = (E²/Δn_st)_E→o. Δn_s is the birefringence extrapolated to infinite field strength.

The molecules show a distribution of relaxation times from 10^-4 to 0.2 sec, which is consistent with expectations for flexible coil molecules. The birefringence and the relaxation times decrease with increasing salt concentrations. They also depend on the field strength and pulse duration in a rather non-reproducible manner, which may be due in part to changes in the composition of the solution or in the molecular structure of the DNA (other than denaturation). Further progress depends on the development of some control over these effects.

Part II

The specificity of the dissociation of reconstituted and native deoxyribonucleohistones (DNH) by monovalent salt solutions has been investigated. A novel zone ultracentrifugation method is used in which the DNH is sedimented as a zone through a preformed salt gradient, superimposed on a stabilizing D₂O (sucrose) density gradient. The results, obtained by scanning the quartz sedimentation tubes in a spectrophotometer, were verified by the conventional, preparative sedimentation technique. Procedures are discussed for the detection of microgram quantities of histones, since low concentrations must be used to prevent excessive aggregation of the DNH.

The data show that major histone fractions are selectively dissociated from DNH by increasing salt concentrations: Lysine rich histone (H I) dissociates gradually between 0.1 and 0.3 F, slightly lysine rich histone (H II) dissociates as a narrow band between 0.35 and 0.5 F, and arginine rich histone (H III, H IV) dissociates gradually above 0.5 F NaClO₄.

The activity of the partially dissociated, native DNH in sustaining RNA synthesis, their mobility and their unusual heat denaturation and renaturation behavior are described. The two-step melting behavior of the material indicates that the histones are non-randomly distributed along the DNA, but the implications are that the uncovered regions are not of gene-size length.