Differing effects of particle size and shape in the infrared and Raman spectra of kaolinite

Infrared (IR) spectra of well-ordered kaolinites generally show four OH-stretching frequencies, near 3697, 3670, 3652 and 3620 cm(-1). Raman spectra of the same kaolinites mostly show an additional band near 3686 cm(-1), which, in the coarsely crystalline Keokuk kaolinite, largely replaces the 3695 cm(-1) band. It is shown that the 3686 cm(-1) band can be ascribed to a transverse optical crystal vibration involving the in-phase stretching vibration of the three inner-surface hydroxyl groups in the unit-cell. Raman exciting radiation, commonly of wavelength near 500 nm, can excite this crystal vibration in crystals of comparable and greater thickness. Infrared studies are usually made on clay-size (<2 mu m) particles, which have mean thicknesses of 30-150 nm. Infrared radiation of wavelength near 2.7 mu m can only excite whole crystal vibrations perpendicular to the plates. The in-phase vibration of inner-surface OH groups in the whole-crystal mode lies at 3697 cm(-1), which is the same frequency as that of the longitudinal optical mode in macroscopic crystals.