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Research accomplishments are presented and include the following: (1) mathematical theory of grain alignment; (2) super-paramagnetic alignment of molecular cloud grains; and (3) theory of grain alignment by ambipolar diffusion.
An introductory account of the semiclassical theory of the S-matrix for molecular collision processes is presented, with special emphasis on electronically nonadiabatic transitions. This theory is based on the incorporation of classical mechanics with quantum superposition, and in practice makes use of the analytic continuation of classical mechanics into the complex space of time domain. The relevant concepts of molecular scattering theory and related dynamical models are described and the formalism is developed and illustrated with simple examples - collinear collision of the A+BC type. The theory is then extended to include the effects of laser-induced nonadiabatic transitions. Two bound continuum processes collisional ionization and collision-induced emission also amenable to the same general semiclassical treatment are discussed.
Thermal configurational data on neat liquids are used to obtain the work of formation of hard spherical cavities of atomic size in six molecular solvents: n-hexane, n-dodecane, n-undecyl alcohol, chloroform, carbon tetrachloride, and water. These results are used to test a recent suggestion that the differences between nonaqueous solvents and liquid water in solvation of inert gases are not principally due to the hydrogen-bonded structure of liquid water but rather to the comparatively small size of the water molecule. The frequencies of occurrence of cavities in liquid water can be meaningfully distinguished from those in the organic solvents. Liquid water has a larger fractional free volume, but that free volume is distributed in smaller packets. With respect to cavity work, water is compared to a solvent of the same molecular density and composed of hard spheres of the same size as the water molecule. That comparison indicates that the hard-sphere liquid finds more ways to configure its free volume in order to accommodate an atomic solute of substantial size and thus, would be more favorable solvent for inert gases. The scaled particle model of inert gas solubility in liquid water predicts cavity works 20% below the numerical data for TIP4P water at 300 K and 1.0 g/cm3 for cavity radii near 2.0 angstroms. It is argued that the sign of this difference is just the sign that ought to be expected and that the magnitude of this difference measures structural differences between water and the directly comparable hard-sphere liquid. In conjunction with previous data, these results indicate that atomic sized cavities should be considered submacroscopic.
Perturbation theory summation method for calculating molecular hydrogen static dipole electric polarizability, using coupled Hartree- Fock approximation
Constraint perturbation calculations for ground state of lithium hydride molecule
Charge carrier mobility in organic semiconductors, described using molecular orbital theory
Closed-cycle operation of molecular adsorption refrigeration systems (MARS) has been demonstrated by using thermally cycled zeolites to adsorb and desorb various gases under pressures of 20-60 atm. This paper develops three aspects of the design theory: the physical theory of molecular adsorption of small molecules such as A, N2, N2O and NH3, the design relations for closed-cycle flow for three or more compressors, and the coefficient of performance. This work is intended to demonstrate nonmechanical gas compression for various cryogenic gases than can compete with mechanical systems with a different mix of advantages and disadvantages.
Evidence is presented that the low temperature anomalies in the hydrogen occlusive behavior of alpha iron can be explained by means of a molecular occlusion theory. This theory proposes that the stable state of the absorbed hydrogen changes from atomic at high temperatures to molecular as the temperature is lowered below a critical value. Theories proposing to explain the anomalous behavior as being due to the capture, at lower temperatures, of hydrogen in traps are shown to be unacceptable.
Slater screening constants in atomic and molecular orbitals
Rarefied gas dynamics - molecular beams and surface interactions, free-molecular flow, fluid mechanics, kinetic theory
Researchers at Penn State have been examining some sonic boom waveforms recorded during overflights by the Air Force which have become available to NASA and its contractors. The quality of the digitized data and the supporting meteorological data was such that one could test the applicability of molecular relaxation theories. In the late sixties, it had been supposed that the finite rise times in the absence of turbulence had neglected the vibrational relaxation of nitrogen molecules. Bass et al. have demonstrated that molecular relaxation definitely gives the correct order of magnitude of the observed rise times. However, the Air Force data in conjunction with the recent steady-state shock profile model theory of Kang and Pierce give the first opportunity to make a detailed quantitative assessment of the molecular relaxation hypothesis. Currently an investigation is ongoing to establish a method of quantifying the distortion of a sonic boom wave from a classic N-wave shape using the Air Force data taken at Edwards AFB in 1987. Using the premise that energy will be conserved approximately for a sonic boom wave both before and after the boom passes through the Earth's turbulent boundary layer, a classic undistorted waveform is constructed from the distorted signature received at the ground. A correlation between the mean-squared deviation of the distorted and undistorted waveforms and the distance the boom travels through the turbulence is sought.
Arc discharge of irradiated mixtures of simple organic and inorganic compounds for development of theory of molecular evolution in protobiological systems
The intensity distribution of bands belonging to six molecular band systems is discussed with special emphasis on their usefulness for intensity calibration of optical systems in the vacuum ultraviolet (1000A Lambda 3000A). The theory of molecular band intensities is outlined and the technique of measuring the spectral response curve is described. Several methods for establishing an absolute intensity calibration are discussed.
Association model theory for thermodynamic properties of nonpolar polymer mixtures with polar solvent
Spherically symmetrical classical scattering theory shows dependence on phase shift through appearance in quantal formulas for scattering amplitude and total cross section
Theoretical simulation of prebiotic chemical processes is an invaluable tool for probing the phenomenon of the evolution of life. Using computational and modeling techniques and guided by analogies from present day systems, we seek to understand the emergence of the genetic apparatus, enzymatic catalysis and protein synthesis under prebiotic conditions. Modeling of the ancestral aminoacyl-tRNA-synthetases (aRS) may provide important clues to the emergence of the genetic code and the protein synthetic machinery. The minimal structural requirements for the catalysis of tRNA aminoacylation are being explored. A formation of an aminoacyl adenylate was studied in the framework of ab initio molecular orbital theory. The role of individual residues in the vicinity of the TyrRS active site was examined, and the effect of all possible amino acids substitutions near the active site was examined. A formation of aminoacyl tRNA was studied by the molecular modeling system SYBYL with the high resolution crystallographic structures of the present day tRNA, aRS's complexes. The ultimate goal is to propose a simple RNA segment that is small enough to be build in the primordial chemical environment but maintains the specificity and catalytic activity of the contemporary RNA enzyme. To understand the mechanism of ribozyme catalyzed reactions, ab initio and semi-empirical (ZINDO) programs were used to investigate the reaction path of transphosphorylation. A special emphasis was placed on the possible catalytic and structural roles played by the coordinated magnesium cation. Both the inline and adjacent mechanisms of transphosphorylation were studied. The structural characteristics of the target helices, particularly a possible role for the G-T pair, is also studied by a molecular dynamics (MD) simulation technique.
The proton affinity of a molecule in the gas phase is a fundamental measure of its basicity and is the factor controlling the course of many ion-molecule reactions. In this article, ab initio molecular orbital theory at the MP4/6-311 ++ G(3df, 3pd) level of theory is demonstrated to predict proton affinities (PA's) for small neutral and anionic bases to within 2 kcal mol-1. Furthermore, the errors are random, indicating that there are likely no systematic errors in either the experimental or theoretical PA's. Also, this level of theory is used to calibrate less sophisticated theoretical models which are suitable for larger molecules; the MP4/6-311 ++ G(2d, 2p) and MP2/6-311 ++ G(d, p) theoretical models should be particularly useful. A procedure for predicting the vibrational frequencies for anion is proposed and applied to CH3-, NH2-, OH-, and CN-.
Ab initio molecular orbital theory is used to estimate the rotational constant for several carbon-chain molecules that are candidates for discovery in interstellar space. These estimated rotational constants can be used in laboratory or astronomical searches for the molecules. The rotational constant for HC13N is estimated to be 0.1073 +/- 0.0002 GHz and its dipole moment 5.4 D. The rotational constant for HC15N is estimated to be 0.0724 GHz, with a somewhat larger uncertainty. The rotational constant of C5O is estimated to be 1.360 +/- 2% GHz and its dipole moment 4.4. D.