I. Quantum mechanics of one-dimensional two-particle models. II. A quantum mechanical treatment of inelastic collisions

Part I

Solutions of Schrödinger’s equation for system of two particles bound in various stationary one-dimensional potential wells and repelling each other with a Coulomb force are obtained by the method of finite differences. The general properties of such systems are worked out in detail for the case of two electrons in an infinite square well. For small well widths (1-10 a.u.) the energy levels lie above those of the noninteresting particle model by as much as a factor of 4, although excitation energies are only half again as great. The analytical form of the solutions is obtained and it is shown that every eigenstate is doubly degenerate due to the “pathological” nature of the one-dimensional Coulomb potential. This degeneracy is verified numerically by the finite-difference method. The properties of the square-well system are compared with those of the free-electron and hard-sphere models; perturbation and variational treatments are also carried out using the hard-sphere Hamiltonian as a zeroth-order approximation. The lowest several finite-difference eigenvalues converge from below with decreasing mesh size to energies below those of the “best” linear variational function consisting of hard-sphere eigenfunctions. The finite-difference solutions in general yield expectation values and matrix elements as accurate as those obtained using the “best” variational function.

The system of two electrons in a parabolic well is also treated by finite differences. In this system it is possible to separate the center-of-mass motion and hence to effect a considerable numerical simplification. It is shown that the pathological one-dimensional Coulomb potential gives rise to doubly degenerate eigenstates for the parabolic well in exactly the same manner as for the infinite square well.

Part II

A general method of treating inelastic collisions quantum mechanically is developed and applied to several one-dimensional models. The formalism is first developed for nonreactive “vibrational” excitations of a bound system by an incident free particle. It is then extended to treat simple exchange reactions of the form A + BC →AB + C. The method consists essentially of finding a set of linearly independent solutions of the Schrödinger equation such that each solution of the set satisfies a distinct, yet arbitrary boundary condition specified in the asymptotic region. These linearly independent solutions are then combined to form a total scattering wavefunction having the correct asymptotic form. The method of finite differences is used to determine the linearly independent functions.

The theory is applied to the impulsive collision of a free particle with a particle bound in (1) an infinite square well and (2) a parabolic well. Calculated transition probabilities agree well with previously obtained values.

Several models for the exchange reaction involving three identical particles are also treated: (1) infinite-square-well potential surface, in which all three particles interact as hard spheres and each two-particle subsystem (i.e. BC and AB) is bound by an attractive infinite-square-well potential; (2) truncated parabolic potential surface, in which the two-particle subsystems are bound by a harmonic oscillator potential which becomes infinite for interparticle separations greater than a certain value; (3) parabolic (untruncated) surface. Although there are no published values with which to compare our reaction probabilities, several independent checks on internal consistency indicate that the results are reliable.

Determination of electronic energy levels of molecules by 90° low energy electron scattering

A review of the theory of electron scattering indicates that low incident beam energies and large scattering angles are the favorable conditions for the observation of optically forbidden transitions in atoms and molecules.

An apparatus capable of yielding electron impact spectra at 90° with incident electron beam energies between 30 and 50 electron volts is described. The resolution of the instrument is about 1 electron volt.

Impact spectra of thirteen molecules have been obtained. Known forbidden transitions to the helium 2³S, the hydrogen b³Ʃ⁺_u, the nitrogen A³Ʃ⁺_u, B³π_g, a’π_g, and C³π_u, the carbon monoxide a³π, the ethylene ᾶ³B_1u, and the benzene ᾶ³B_1u states from the corresponding ground states have been observed.

In addition, singlet-triplet vertical transitions in acetylene, propyne, propadiene, norbornadiene and quadricyclene, peaking at 5.9, 5.9, 4.5, 3.8, and 4.0 ev (±0.2 ev), respectively, have been observed and assigned for the first time.

I. Proton magnetic resonance of polynucleotides and transfer RNA. II. Electron spin relaxation studies of manganese (II) complexes in acetonitrile

Part I. Proton Magnetic Resonance of Polynucleotides and Transfer RNA.

Proton magnetic resonance was used to follow the temperature dependent intramolecular stacking of the bases in the polynucleotides of adenine and cytosine. Analysis of the results on the basis of a two state stacked-unstacked model yielded values of -4.5 kcal/mole and -9.5 kcal/mole for the enthalpies of stacking in polyadenylic and polycytidylic acid, respectively.

The interaction of purine with these molecules was also studied by pmr. Analysis of these results and the comparison of the thermal unstacking of polynucleotides and short chain nucleotides indicates that the bases contained in stacks within the long chain poly nucleotides are, on the average, closer together than the bases contained in stacks in the short chain nucleotides.

Temperature and purine studies were also carried out with an aqueous solution of formylmethionine transfer ribonucleic acid. Comparison of these results with the results of similar experiments with the homopolynucleotides of adenine, cytosine and uracil indicate that the purine is probably intercalating into loop regions of the molecule.

The solvent denaturation of phenylalanine transfer ribonucleic acid was followed by pmr. In a solvent mixture containing 83 volume per cent dimethylsulf oxide and 17 per cent deuterium oxide, the tRNA molecule is rendered quite flexible. It is possible to resolve resonances of protons on the common bases and on certain modified bases.

Part II. Electron Spin Relaxation Studies of Manganese (II) Complexes in Acetonitrile.

The electron paramagnetic resonance spectra of three Mn⁺² complexes, [Mn(CH₃CN)₆]⁺², [MnCl₄]^-2, and [MnBr₄]^-2, in acetonitrile were studied in detail. The objective of this study was to relate changes in the effective spin Hamiltonian parameters and the resonance line widths to the structure of these molecular complexes as well as to dynamical processes in solution.

Of the three systems studied, the results obtained from the [Mn(CH₃CN)₆]⁺² system were the most straight-forward to interpret. Resonance broadening attributable to manganese spin-spin dipolar interactions was observed as the manganese concentration was increased.

In the [MnCl₄]^-2 system, solvent fluctuations and dynamical ion-pairing appear to be significant in determining electron spin relaxation.

In the [MnBr₄]^-2 system, solvent fluctuations, ion-pairing, and Br- ligand exchange provide the principal means of electron spin relaxation. It was also found that the spin relaxation in this system is dependent upon the field strength and is directly related to the manganese concentration. A relaxation theory based on a two state collisional model was developed to account for the observed behavior.

Relativistic velocity - potential hydrodynamics and stellar stability

The equations of relativistic, perfect-fluid hydrodynamics are cast in Eulerian form using six scalar "velocity-potential" fields, each of which has an equation of evolution. These equations determine the motion of the fluid through the equation

U_ʋ=µ^-1 (ø,_ʋ + αβ,_ʋ + ƟS,_ʋ).

Einstein's equations and the velocity-potential hydrodynamical equations follow from a variational principle whose action is

I = (R + 16π p) (-g)^1/2 d⁴x,

where R is the scalar curvature of spacetime and p is the pressure of the fluid. These equations are also cast into Hamiltonian form, with Hamiltonian density –T₀⁰ (-g^oo)^-1/2.

The second variation of the action is used as the Lagrangian governing the evolution of small perturbations of differentially rotating stellar models. In Newtonian gravity this leads to linear dynamical stability criteria already known. In general relativity it leads to a new sufficient condition for the stability of such models against arbitrary perturbations.

By introducing three scalar fields defined by

ρ ᵴ = ∇λ + ∇x(xi + ∇xɣi)

(where ᵴ is the vector displacement of the perturbed fluid element, ρ is the mass-density, and i, is an arbitrary vector), the Newtonian stability criteria are greatly simplified for the purpose of practical applications. The relativistic stability criterion is not yet in a form that permits practical calculations, but ways to place it in such a form are discussed.