Surface enhanced Raman scattering from mildly roughened surfaces: variation of signal with metal grain size

The intensity of surface enhanced Raman scattering from benzoic acid derivatives on mildly roughened, thermally evaporated Ag films shows a remarkably strong dependence on metal grain size. Large grained (slowly deposited) films give a superior response, by up to a factor of 10, to small grained (quickly deposited) films, with films of intermediate grain size yielding intermediate results. The optical field amplification underlying the enhancement mechanism is due to the excitation of surface plasmon polaritons (SPPs). Since surface roughness characteristics, as determined by STM, remain relatively constant as a function of deposition rate, it is argued that the contrast in Raman scattering is due to differences in elastic grain boundary scattering of SPPs (leading to different degrees of internal SPP damping), rather than differences in the interaction of SPPs with surface inhomogeneities.     

Equilibrium time correlation functions in the low-density limit

We consider a system of hard spheres in thermal equilibrium. Using Lanford's result about the convergence of the solutions of the BBGKY hierarchy to the solutions of the Boltzmann hierarchy, we show that in the low-density limit (Boltzmann-Grad limit): (i) the total time correlation function is governed by the linearized Boltzmann equation (proved to be valid for short times), (ii) the self time correlation function, equivalently the distribution of a tagged particle in an equilibrium fluid, is governed by the Rayleigh-Boltzmann equation (proved to be valid for all times). In the latter case the fluid (not including the tagged particle) is to zeroth order in thermal equilibrium and to first order its distribution is governed by a combination of the Rayleigh-Boltzmann equation and the linearized Boltzmann equation (proved to be valid for short times).Supported in part by NSF Grant PHY 78-22302.     

The not-so-peculiar case of calcium oxide: a weakness in atomic natural orbital basis sets for calcium

Atomic natural orbital (ANO) basis sets for calcium may produce surprisingly poor atomic and molecular properties and energetics. The weaknesses in these basis sets may be traced primarily to deficiencies within the sets of d functions which are incapable of effectively correlating the 3s and 3p electrons. Examples are given which show that addition of tight d functions to the ANO basis is required to achieve qualitatively correct energetics and structures for conventionally bonded calcium compounds.     

Unsolvable Problems About Small Cancellation and Word Hyperbolic Groups

We apply a construction of Rips to show that a number of algorithmicproblems concerning certain small cancellation groups and, inparticular, word hyperbolic groups, are recursively unsolvable.Given any integer k > 2, there is no algorithm to determinewhether or not any small cancellation group can be generatedby either two elements or more than k elements. There is a smallcancellation group E such that there is no algorithm to determinewhether or not any finitely generated subgroup of E is all ofE, or is finitely presented, or has a finitely generated secondintegral homology group.     

Emission Mössbauer studies of the magnetoresistive compound, La0.7Sr0.3MnO3

The magnetic behavior of the Sr_0.3 manganite is studied using a local microprobe, ⁵⁷Co. In contrast with Ca substituted manganites, a much larger fraction of the material exhibits short-range order with superparamagnetic-like behavior even at 80 K. The differences in behavior are attributed to the large mismatch between the ionic radii of La⁺³ and the divalent substituent Sr⁺², which introduces anharmonicity in local vibrations. In common with all other compounds exhibiting negative bulk magnetoresistivity, the Sr_0.3 compound also exhibits very marked softening of lattice as one approaches T_c from below. Application of an external magnetic field results in coalescing of nanosized magnetic clusters to form larger ones with better alignment of spins.     

Electrical detection of nuclear spin echoes

We show, via a straightforward calculation, that it is feasible to detect nuclear spin echoes in a ferromagnetic thin film by electrical means. The detection scheme is based on the deflection of the electronic magnetization when the nuclear magnetization reforms during an echo. This deflection is observed as a time-dependent magnetoresistive signal.     

Observation of Optical Second Harmonic Generation in Wet-Spun Films of Na-DNA

The observation of optical second harmonic generation (SHG) from wetspun films of Na-DNA is reported. The SHG signal is stronger at a relative humidity of 92% (corresponding to the B conformation of Na-DNA) than at low humidity of -33% (corresponding to a disordered conformation of Na-DNA). The strength of the SHG signal is also dependent on the orientation of the incident laser beam polarization with respect to the DNA helical axes.     

Design and development of a fiber-optic immunosensor utilizing near-infrared fluorophores

The design and application of a fluorescent fiber-optic immunosensor (FFOI) are reported. The FFOI is utilized for the detection of antibody/antigen binding within the near-infrared (NIR) spectral region. The technique is developed through the combined use of fiber-optic, semiconductor laser-excitation, fluorescence detection, NIR dye, and immunochemical techniques. The antibody is immobilized on the FFOI and utilized as a recognition component for trace amounts of specific antigen. The FFOI is constructed to utilize an antibody sandwich technique. The assay involves the immobilization of the capture antibody on the sensing tip of the FFOI followed by the exposure of the immobilized sensing tip to the antigen. The antigen-coated FFOI is then introduced to a second antibody previously labeled with the NIR dye. Typical measurements are performed in about 15 min. A semiconductor laser provides the excitation (780 nm) of the immune complex. The resulting emission is detected by a silicon photodiode detector (820 nm). The intensity of the resulting fluorescence is directly proportional to the concentration of the antigen. The sensitivity of the analysis reaches 10 ng/ml and the response time is 10–15 min.