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E J Ayars

Publications and source records attributed to E J Ayars.

3 recordsLinked to original sources

The effects of probe boundary conditions and propagation on nano-Raman spectroscopy.

Raman spectra obtained in the near-field, with collection of the Raman-shifted light in reflection, show selective enhancement of vibrational modes. We show that the boundary conditions for an electric field near a metal surface affect propagation of the reflected signal and lead to this selection. The enhancement of certain Raman forbidden vibrations is explained by the presence of an electric field gradient near the metal-apertured fibre probe.

Journal Article↗

Fundamental differences between micro- and nano-Raman spectroscopy.

Electric field polarization orientations and gradients close to near-field scanning optical microscope (NSOM) probes render nano-Raman fundamentally different from micro-Raman spectroscopy. With x-polarized light incident through an NSOM aperture, transmitted light has x, y and z components allowing nano-Raman investigators to probe a variety of polarization configurations. In addition, the strong field gradients in the near-field of a NSOM probe lead to a breakdown of the assumption of micro-Raman spectroscopy that the field is constant over molecular dimensions. Thus, for nano-Raman spectroscopy with an NSOM, selection rules allow for the detection of active modes with intensity dependent on the field gradient. These modes can have similar activity as infra-red absorption modes. The mechanism can also explain the origin and intensity of some Raman modes observed in surface enhanced Raman spectroscopy.

Journal Article↗

Electric field gradient effects in raman spectroscopy.

Raman spectra of materials subject to strong electric field gradients, such as those present near a metal surface, can show significantly altered selection rules. We describe a new mechanism by which the field gradients can produce Raman-like lines. We develop a theoretical model for this "gradient-field Raman" effect, discuss selection rules, and compare to other mechanisms that produce Raman-like lines in the presence of strong field gradients. The mechanism can explain the origin and intensity of some Raman modes observed in SERS and through a near-field optical microscope (NSOM-Raman).

Journal Article↗