This study examines the effects of particle sizes between 3 and 121 μm on the fundamental vibrations of the [CO3(2-)] anion in calcite [CaCO3] as analyzed by total attenuated reflectance infrared spectroscopy (ATR-IR) and Raman spectroscopy (RS). The ATR-IR absorbance intensity ratios of the [ν4/ν3] [712 cm(-1)/1393 cm(-1)], [ν4/ν2] [712 cm(-1)/871 cm(-1)], and [ν2/ν3] [871 cm(-1)/1393 cm(-1)] share the same profile for grain size fractions 121 μm through to 42 μm mode. Between 42 and 3 μm mode the three ratios sharply decline in a systematic manner, consistent with a nonuniform decrease in spectral contrast of the [CO3(2-)] internal modes.
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