Raman and FTIR Spectroscopy of Synthetic Amphiboles: I. The OH Librational Bands and the Determination of the OH-F Content of Richterites via Raman Spectroscopy

Abstract

Unpolarized FTIR and Raman spectra were collected in the regions 4000–4600 cm–1 (NIR) and 100–4000 cm–1 from previously synthesized and characterized amphiboles in the systems richterite–fluoro-richterite, potassic-richterite–potassic-fluoro-richterite, rubidium-richterite–rubidium-fluoro-richterite, and potassic-richterite–deuterated potassic-richterite. The NIR spectra of Na-, K-, and Rb-richterites have peaks at 4325, 4210 cm–1, and 3735–3730 cm–1. All three peaks decrease in intensity with increasing F content, indicating that the higher-energy peaks are combination bands involving the principal OH-stretch at 3735–3730 cm–1 and two OH-libration modes, the frequencies of which can be calculated from the relation ωcombination ≈ ωOH + ωlibration; these are 590 and 475 cm–1, respectively. The FTIR spectra of the richterite–fluoro-richterite and potassic-richterite–potassic-fluoro-richterite series show decreasing intensity and eventual disappearance of the band at ∼600 cm–1 with increasing F in accord with the assignment of this band as due to OH-libration. Raman spectra of the potassic-richterite–deuterated potassic-richterite amphiboles in the low-energy region show the disappearance of two peaks at 585 and 473 cm–1 that we have assigned to OH-libration modes. Collectively, these spectroscopic results indicate that there are two OH-libration modes at ∼590 and ∼475 cm–1 in these synthetic richterites and, by implication, in all monoclinic OH-bearing amphiboles with filled A sites. Similarly to FTIR, the relative intensities of the stretching modes associated with OH-A-OH and OH-A-F local configurations in the Raman spectra provide a reliable estimation of the F content in these A site-filled amphiboles.