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At least 55 records · Page 3

Semi-Annual Report: October 15, 1961

Investigations are proposed involving an experimental and theoretical program designed to investigate various properties of the structure of helium both in its atomic form and in the aggregates of the liquid and solid states. The key to the possibilities of performing the experiments lies in the relatively weak electric fields existing in liquid and solid helium and the possibility of producing external fields almost comparable with the internal fields. It is proposed to examine a) the melting pressure curve for helium as a function of electric field b) the dielectric constant of helium as a function of pressure and electric field c) in future, the effect of electric fields on the lambda transition. From the results of these experiments one would expect to be able to gather at least corroborative evidence on a) the crystal structure of solid helium on b) the effect of the Van der Waal interaction of the electric polarizability of helium, c) the possibility of producing helium molecules d) the effective volume available to helium atoms in the liquid and possibly e) the effect of particle interactions on the Bose-Einstein condensation.

HELIUM↗

Some Theoretical Aspect of Cryosorption

When a gas or vapor is allowed to come to equilibrium with a solid surface, the concentration of gas molecules is always found to be greater in the immediate vicinity of the surface than in the free gas phase, regardless of the nature of the gas or of the surface. The process by which this surface excess is formed is termed adsorption. In any solid, the atoms at the surface are subject to unbalanced forces of attraction normal to the surface plane; the balance of forces is partially restored by the adsorption of gas molecules. If the forces responsible for adsorption are of van der Waals type, the process is called physical adsorption. Furthermore, if the solid (and its surface) are maintained at relatively low temperatures (say 50°K or below), the term cryosorption is used.

ADSORPTION↗

Broadening of the D lines and the relaxation of the resonance levels of sodium due to collisions with helium.

Calculated potentials for the NaHe molecule are used to obtain collision-induced widths and shifts for the sodium D lines together with cross sections for fine-structure transitions and the relaxation of the multipole polarizations of the resonance levels. The atomic collision is treated in an adiabatic approximation in which the colliding atoms form a molecular system which rotates during the collision. We find the resonance lines to be broadened equally and to be approximately 70% wider, and with associated shifts of an order of magnitude smaller, than expected on the basis of van der Waals forces. The dependence of the cross sections for relaxation of the multipole polarizations of the resonance levels on the molecular-coupling conditions and the rotation of the system during collision is discussed and indicates a limitation of the sum rule for these cross sections.

Lewis, E. L.↗

Phase equilibria in molecular hydrogen-helium mixtures at high pressures

Experiments on phase behavior in hydrogen-helium mixtures have been carried out at pressures up to 9.3 kilobars, at temperatures from 26 to 100 K. Two distinct fluid phases are shown to exist at supercritical temperatures and high pressures. Both the trend of the experimental results and an analysis based on the van der Waals theory of mixtures suggest that this fluid-fluid phase separation persists at temperatures and pressures beyond the range of these experiments, perhaps even to the limits of stability of the molecular phases. The results confirm earlier predictions concerning the form of the hydrogen-helium phase diagram in the region of pressure-induced solidification of the molecular phases at supercritical temperatures. The implications of this phase diagram for planetary interiors are discussed.

Streett, W. B.↗

A theoretical study of optical contact of vitreous silica

Optical contact has been proposed as a method of bonding quartz parts of the Stanford relativity satellite. The theory of the van der Waals force is outlined and applied to the problem of optical contact. The effect of various contaminations is discussed and a program of experimentation for further study of the problem is presented.

Barber, T. D.↗

Partition function corrections

The vibration-rotation interaction coupling in diatomic molecules is analyzed and first-order expressions for the energy levels are deduced. Corrections to the partition function to account for this coupling are derived. The effects of long-range intermolecular forces due to induced dipole-induced dipole interactions, dipole-induced dipole interactions, charge-dipole interactions, and charge-charge interactions are considered. London's quantized oscillator model of the induced dipole-induced dipole interaction is developed. The partition function including effects of such dispersion forces is derived and is shown to lead to the virial equation of state. For a model combining the hard sphere and long-range attractive type potentials, this is found to lead to the van der Waals equation of state. The equation of state near the critical point is presented in reduced form (thermodynamic variables expressed in units of critical point values). Finally, approximate corrections to the electronic partition functions are derived to account for perturbations of excited electronic states induced by neighboring neutral particles, heavy ions, and fast electron collisions.

Source record↗

Shear strength of metal-sapphire contacts

The shear strength of polycrystalline Ag, Cu, Ni, and Fe contacts on clean (0001) sapphire has been studied in ultrahigh vacuum. Both clean metal surfaces and surfaces exposed to O2, Cl2, and C2H4 were used. The results indicate that there are two sources of strength of Al2O3-metal contacts: an intrinsic one that depends on the particular clean metal in contact with Al2O3 and an additional one due to intermediate films. The shear strength of the clean metal contacts correlated directly with the free energy of oxide formation for the lowest metal oxide, in accord with the hypothesis that a chemical bond is formed between metal cations and oxygen anions in the sapphire surface. Contacts formed by metals exposed to chlorine exhibited uniformly low shear strength indicative of van der Waals bonding between chlorinated metal surfaces and sapphire. Contacts formed by metals exposed to oxygen exhibited enhanced shear strength, in accord with the hypothesis that an intermediate oxide layer increases interfacial strength.

Pepper, S. V.↗

Effect of adsorbed films on friction of Al2O3-metal systems

The kinetic friction of polycrystalline Al2O3 sliding on Cu, Ni, and Fe in ultrahigh vacuum was studied as a function of the surface chemistry of the metal. Clean metal surfaces were exposed to O2, Cl2, C2H4, and C2H3Cl, and the change in friction due to the adsorbed species was observed. Auger electron spectroscopy assessed the elemental composition of the metal surface. It was found that the systems exposed to Cl2 exhibited low friction, interpreted as the van der Waals force between the Al2O3 and metal chloride. The generation of metal oxide by oxygen exposures resulted in an increase in friction, interpreted as due to strong interfacial bonds established by reaction of metal oxide with Al2O3 to form the complex oxide (spinel). The only effect of C2H4 was to increase the friction of the Fe system, but C2H3Cl exposures decreases friction in both Ni and Fe systems, indicating the dominance of the chlorine over the ethylene complex on the surface

Pepper, S. V.↗

FLUID: A numerical interpolation procedure for obtaining thermodynamic and transport properties of fluids

A computer program subroutine, FLUID, was developed to calculate thermodynamic and transport properties of pure fluid substances. It provides for determining the thermodynamic state from assigned values for temperature-density, pressure-density, temperature-pressure, pressure-entropy, or pressure-enthalpy. Liquid or two-phase (liquid-gas) conditions are considered as well as the gas phase. A van der Waals model is used to obtain approximate state values; these values are then corrected for real gas effects by model-correction factors obtained from tables based on experimental data. Saturation conditions, specific heat, entropy, and enthalpy data are included in the tables for each gas. Since these tables are external to the FLUID subroutine itself, FLUID can implement any gas for which a set of tables has been generated. (A setup phase is used to establish pointers dynamically to the tables for a specific gas.) Data-table preparation is described. FLUID is available in both SFTRAN and FORTRAN

Fessler, T. E.↗

The effect of the liquid-solid system properties on the interline heat transfer coefficient

A theoretical procedure to determine the heat transfer characteristics of the interline region of an evaporating meniscus using the macroscopic optical and thermophysical properties of the system is outlined. The analysis is based on the premise that the interline transport processes are controlled by the London-van der Waals forces between condensed phases (solid and liquid). The procedure is used to compare the relative size of the interline heat sink of various systems using a constant heat flux model. This solution demonstrates the importance of the interline heat flow number which is evaluated for various systems. The heat transfer characteristics of the decane-steel system are numerically compared with those of the carbon tetrachloride-quartz system.

Wayner, P. C., Jr.↗

A shock tube study of line broadening in a temperature range of 6100 to 8300 K

Line widths of the Ca(II) 3968 A and Na(I) 5890 A resonance lines broadened by electric microfields in a plasma were measured. A pressure-driven shock tube was used as the light source. Radiation from the equilibrium region behind the reflected shock wave was studied using a rapid scanning Fabry-Perot interferometer. Electron and argon atom densities of about 8 x 10 to the 16th and 1 x 10 to the 19th/cu cm, respectively, were achieved at the relatively low temperature of around 7500 K by vaporizing a cesium powder that had been added to the shock tube as a solid aerosol in argon gas. The measured line widths were predominantly Stark broadened by the electrons and ions in the plasma, although Doppler, van der Waals, instrument function and optical depth effects had to be taken into account.

Baur, J. F.↗

Width of a planetary ring system and the C-ring of Saturn

The growth of particles in a planetary ring system is considered with reference to the C-ring of Saturn. Small particles arising from various sources collide with and temporarily adhere to larger particles, and the paper presents a mathematical analysis of the conditions under which the small particles will stay long enough on the surface of the larger ones so that a permanent bond will develop. It is initially assumed that the only force acting between the particles is gravitational attraction, and upper and lower limits for the width of a planetary ring are determined. The effects of van der Waals forces are then considered.

Smoluchowski, R.↗

Extensions to the classical calculation of the effect of mutual shadowing in diffuse reflection

The classical method for accounting for the mutual shadowing among closely packed particles in multiple scattering calculations is extended in the following ways. (1) By modeling the particle distribution by a Poisson process with a varying density parameter, a 'Van der Waals' type approximation allows extension to a greater fractional volume density, D. In this case it is only required that D squared be much less than 1 instead of D being much less than 1. (2) In the case that the particle distribution is not uniform the classical calculation may be weighted by the pair correlation function of the distribution. (3) The use of the Markov chain formalism for radiative transfer allows inclusion of the effect of shadowing for two orders of scattering. For conditions such as might apply in Saturn's rings, the inclusion of this effect makes less than a 0.1% difference in the calculated phase curves, compared to previous calculations which have included shadowing only in the first scattering. The latter are thus shown to be quite accurate.

Esposito, L. W.↗

The dispersed fluorescence spectrum of NaAr - Ground and excited state potential curves

Potential curves for the ground state and the first excited state of NaAr were determined. The van der Waals molecule NaAr was prepared by supersonic free jet expansion of a mixture of sodium, argon, and helium. The electronic transition from the ground state to the first excited state A2pi was excited by a tunable dye laser and the resulting fluorescence was studied. The dispersed fluorescence spectra show discrete and diffuse features, corresponding to transitions from excited vibrational levels of the A state to bound and unbound levels of the x state. The characteristic reflection structure in the bound-free spectra permits an unambiguous assignment of the vibrational numbering in the A state, and this assignment together with previously measured spectroscopic constants are used to calculate the potential curve of the A state. The discrete structure in the fluorescence spectra is used to determine the potential curve of the x state in the well region, and the repulsive part of the X curve is then deduced through trial-and-error simulation of the bound-free spectra.

Tellinghuisen, J.↗

Investigation of the 1-0 pressure-induced vibrational absorption spectrum of hydrogen at temperatures below ambient

A theoretical fit has been made to laboratory measurements of the 1-0 collisionally induced H2 absorption band over a temperature range of 100-273 K and for densities up to 22 amagats. Both the Birnbaum-Cohen and the MacTaggert-Hunt line shape profiles were used. In addition, an intermolecular potential of either a Lennard-Jones 6-12 or a Morse-spline-van der Waals has been used for each line shape. The best fit resulted in a chi-square of 5%. Line widths have also been derived as a function of temperature. The lifetimes of the states were calculated.

Goorvitch, D.↗

Theoretical calculation of low-lying states of NaAr and NaXe

Potential curves as well as dipole moments and linking transition moments are calculated for the ground X 2 Sigma + and low lying excited A 2 Pi, B 2 Sigma +, C 2 Sigma +, (4) 2 Sigma +, (2) 2 Pi and (1) 2 Delta states of NaAr and NaXe. Calculations are performed using a self-consistent field plus configuration-interaction procedure with the core electrons replaced by an ab initio effective core potential. The potential curves obtained are found to be considerably less repulsive than the semiempirical curves of Pascale and Vandeplanque (1974) and to agree well with existing experimental data, although the binding energies of those states having potential minima due to van der Waals interactions are underestimated. Emission bands are also calculated for the X 2 Sigma + - C 2 Sigma + excimer transitions of NaAr and NaXe using the calculated transition moments and potential curves, and shown to agree well with experiment on the short-wavelength side of the maximum.

Laskowski, B. C.↗