On the basis of different types of experiments, the authors develop implicitly the model of surface-enhanced Raman scattering (SERS) of adsorbates on metal surfaces. The long-range enhancement by resonances of the macroscopic laser and Stokes field is separated quantitatively from the metal electron-mediated resonance Raman effect. The latter mechanism proceeds by increased electron-photon coupling at an atomically rough surface and by temporary charge transfer to orbitals of the adsorbates. This model can account for the chemical specificity and vibrational selectivity of SERS and (partly) for the SERS specificity of the various metals.

https://iopscience.iop.org/article/10.1088/0953-8984/4/5/001/pdf

Surface-enhanced Raman scattering

As part of a systematic study of approximations commonly made in solutions of the Boltzmann equation for electrons in molecular gases, we have investigated the effects of anisotropic scattering on electron transport coefficients in ${\mathrm{N}}_{2}$ and have extended our study of the multiterm expansion technique to higher E/n. A critical survey of published data yields a set of differential and integral cross sections for electron energies from 0.003 to ${10}^{4}$ eV. For electric-field--to--gas-density ratios E/n between 10 and 500 Td (1 Td${=10}^{\mathrm{\ensuremath{-}}21}$ V ${\mathrm{m}}^{2}$), the changes in the commonly measured transport and reaction coefficients resulting from the introduction of anisotropic elastic and inelastic scattering, while keeping the elastic momentum-transfer cross section constant, are less than 1%.These calculations were made with use of the multiterm spherical-harmonic expansion solution of the Boltzmann equation. For 500lE/nl1500 Td the changes in scattering anisotropy cause changes in transport and reaction coefficients which increase with E/n to about 10%. The errors in drift velocity, mean energy, and the reaction coefficients resulting from the use of the two-term spherical-harmonic expansion rather than a six-term expansion are less than 3% at 1500 Td.However, the errors in the diffusion coefficients become large (g25%) at our highest E/n. The calculated transport coefficients are in generally good agreement with experiment for E/n less than 300 Td, but the differences increase at higher E/n. The importance of proper interpretation of ionization and excitation experiments at high E/n is illustrated by calculations which model either an exponential growth of density in time or an exponential growth with position. The calculated ionization coefficients are low compared to most experiments for E/n less than 200 Td. At E/ng600 Td the agreement is good for the spatial growth experiments, but the calculated values are below experiment from the temporal growth experiments. The calculated excitation coefficients are generally higher than experiment at low and high E/n but in agreement with experiment at E/n near 150 Td.

Anisotropic scattering of electrons by N2 and its effect on electron transport.

A tomographic inversion is used to analyze measurements of the auroral atomic oxygen emission line at 6300 A made by the atmosphere explorer visible airglow experiment. A comparison is made between emission altitude profiles and the results from an electron transport and chemical reaction model. Measurements of the energetic electron flux, neutral composition, ion composition, and electron density are incorporated in the model.

The auroral 6300 Å emission: Observations and modeling

Electron-molecule scattering cross-sections. I. Experimental techniques and data for diatomic molecules

Publisher Summary This chapter discusses resonance and threshold phenomena in low-energy electron collisions with molecules and clusters. Low-energy collisions of electrons with atoms and molecules are among the most important elementary processes in gaseous environments such as discharges, arcs, gas lasers, gaseous dielectrics and the earth's atmosphere. The dynamics behavior of low-energy electron-molecule collisions is discussed. The dynamical behavior of slow electrons traversing gases is to a large extent determined by two effects: the energy dependent evolution of the scattering phases for the relevant partial waves and the influence of temporary negative ion states (resonances). Some aspects of resonance and threshold phenomena are discussed. The theoretical description of electron-molecule collisions generally requires an adequate description of electronic, vibrational and rotational degrees of freedom. However, if the typical collision time is short compared to the rotational period, the molecule can be treated as having a fixed orientation during the collision process, and the result for the cross-section can be averaged over orientations. Treatment of vibrational dynamics is usually more important and more challenging to the theory. In the electron energy region important for applications, many inelastic processes such as vibrational excitation and dissociative electron attachment are driven by negative-ion resonances. The theoretical description of vibrational dynamics in these cases is usually based on the nonlocal complex potential describing the nuclear motion in the intermediate negative-ion state.

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D.F. Register

Papers

Electron scattering by molecules II. Experimental methods and data