Isotopic study of the mechanism of ozone formation

The mechanism of ozone formation has been studied using ¹⁶O and ¹⁸O₂. High-resolution microwave spectroscopy was used to measure the amounts of the isotopomeric ozone species formed. The study is hampered by the very rapid exchange process between the reactants, that tends to scramble the isotopes and hence give a 2:1 statistical ratio between the two possible isotopomers. We have found a strategy to come around this difficulty and conclude that the mechanism is a simple end-on-addition.     

Construction of orbital angular momentum eigenfunctions for many-particle systems by harmonic projection

Formulas are derived which allow the direct construction of total orbital angular momentum eigenfunctions for many-particle systems without the use of Clebsch–Gordan coefficients. One of the equations is closely analogous to Dirac' identity for the total spin operator. This equation describes the action of L² on a function of the particle coordinates in terms of a class operator of the symmetric group and a "contraction operator." A general projection operator for constructing symmetric eigenfunctions of L² is presented.     

Resistivity of positive-J spin glasses: Study ofLaGd under hydrostatic pressure

Results of a new calculation of the resistivity in the noise model of spin glasses, based on the –J S interaction forpositive J, are compared with measurements of the resistivity in an fcc La-8at% Gd alloy under hydrostatic pressures up to 12 kbar, the first positive-J resistivity investigations under pressure. A positive value ofJ that decreases with increasing pressure, in accord with other experiments, leads to quantitative agreement between theory and experiment if one uses a large electronic density of states at the Fermi energy, in accord with specific heat measurements and electronic band structure calculations in fcc La. Impurity potential scattering is found to contribute significantly to the resistivity. Its size and pressure variation is determined.This work is supported in part by the Deutsche Forschungs-gemeinschaft.     

Stress relaxation behavior of soda-lime glass between the transformation and softening temperatures

The compressive stress relaxation modulus of a container glass composition was investigated over a wide range of strain, time, modulus, and temperature. It is shown that the glass behaves in a linear viscoelastic manner up to a 2% strain level, and that the relaxation modulus is a smooth function of time, with no pseudo-rubbery plateau apparent down to a modulus of 10⁸ dyn/cm². The data cover roughly five decades of modulus, five decades of time, and a temperature range of 150° C above the glass transition, T_g = 536°C. Within experimental error, the effect of temperature on the stress relaxation behavior is to simply shift the modulus-time curves along the time axis with no change in shape. Temperature dependent shift factor data are expressed in terms of the WLF relation, and are shown to be in good agreement with data found in the literature for other silicate compositions. Viscosity data derived from the generated stress relaxation data agree well with data obtained by more direct methods.     

Projections of quantum observables onto classical degrees of freedom in mixed quantum-classical simulations: understanding linear response failure for the photoexcited hydrated electron

We present a general analytic method for understanding how specific motions of a classical bath influence the dynamics of quantum-mechanical observables in mixed quantum-classical molecular dynamics simulations. We apply our method and develop expressions for the special case of quantum solvation, allowing us to examine how specific classical solvent motions couple to the equilibrium energy fluctuations and nonequilibrium energy relaxation of a quantum-mechanical solute. As a first application of our formalism, we investigate the motions of classical water underlying the equilibrium and nonequilibrium excited-state solvent response functions of the hydrated electron; the results allow us to explain why the linear response approximation fails for this system.     

Three-Body Phase Shift in One-Dimensional 2 + 1 Scattering

For a model of three particles on a line, subject to attractive delta-function interactions, we consider the phase shift. We do this from the point of view of the calculation of the S-matrix in a hyperspherical adiabatic basis (an adiabatic S-matrix), and for energies ranging from the (negative) energy of the two-body bound state to a total energy of zero. We derive analytical expansions and present numerical work, for different approximations, and compare with the exact results that we obtain from the work of McGuire, whose model we have borrowed. We show that the simplest adiabatic approximation gives results that are qualitatively wrong, but that better approximations yield, for most of our range, excellent agreement with the exact result. Understanding the threshold behaviour, however, requires a zero-energy three-body bound state, or resonance, previously unsuspected for this model. The methods developed for the case of the simplest adiabatic approximation also yield threshold and low-energy results applicable to the two-body problem in two dimensions. Received December 23, 1996; revised May 13, 1997; accepted for publication June 19, 1997     

High-resolution infrared and theoretical study of gaseous 1,2,5-selenadiazole in the 600-1400 cm range

The Fourier transform gas-phase IR spectrum of natural isotopic 1,2,5-selenadiazole, C₂H₂N₂Se, has been recorded with a resolution of ca. 0.0025 cm⁻¹ in the wavenumber region 600-1400 cm⁻¹. The three a-type bands, ν₂ (A₁), ν₄ (A₁), ν₅ (A₁), the two b-type bands ν₁₁ (B₁), ν₁₂ (B₁), and the c-type band ν₁₄ (B₂) for each of the isotopologues C₂H₂N₂⁸⁰Se and C₂H₂N₂⁷⁸Se have been analyzed using the Watson model. Ground state rotational and quartic centrifugal distortion constants as well as upper state spectroscopic constants have been obtained from the fits. The rotational constants, harmonic and anharmonic frequencies, and vibration-rotation constants (alphas, ) have been predicted by quantum chemical calculations using a cc-pVTZ basis at the MP2 and B3LYP methodology levels, and compared with the present experimental data. Although the rotation constants are marginally closer to experiment from the MP2 calculations, in general the B3LYP frequencies and alphas are closer to experiment.     

The high-resolution infrared spectrum of pyrrole between 900 and 1500 cm revisited

The Fourier transform gas-phase infrared spectrum of pyrrole, C₄H₅N, has been recorded with a resolution of ca. 0.003 cm⁻¹ in the 900-1500 cm⁻¹ spectral region. Four fundamental bands, ν₈(A₁; 1016.9 cm⁻¹), ν₂₃(B₂; 1049.1 cm⁻¹), ν₇(A₁; 1074.6 cm⁻¹), ν₂₀(B₂; 1424.4 cm⁻¹) and the overtone band 2ν₁₆(A₁; 962.7 cm⁻¹) have been analysed using the Watson model. The ν₈ and 2ν₁₆ bands are unperturbed; the ν₇ and ν₂₃ bands are locally perturbed, while the ν₂₀ band is globally perturbed by weak c-Coriolis resonance. Upper state vibrational term values, and rotational and centrifugal distortion constants, have been obtained from fits using S-reduction and I^r-representation as well as A-reduction and III^r-representation. A set of ground state rotational and centrifugal distortion constants using A-reduction was obtained from a simultaneous fit of ground state combination differences from all five bands and previous microwave and millimetre-wave data.     

Nanoscale zeeman localization of charge carriers in diluted magnetic semiconductor-permalloy hybrids

We investigate the possibility of charge carrier localization in magnetic semiconductors due to the presence of a highly inhomogeneous external magnetic field. As an example, we study in detail the properties of a magnetic semiconductor-permalloy disk hybrid system. We find that the giant Zeeman response of the magnetic semiconductor in conjunction with the highly nonuniform magnetic field created by the vortex state of a permalloy disk can lead to Zeeman localized states at the interface of the two materials. These trapped states are chiral, with chirality controlled by the orientation of the core magnetization of the permalloy disk. We calculate the energy spectrum and the eigenstates of these Zeeman localized states, and discuss their experimental signatures in spectroscopic probes.