Abstract

The Raman spectrum of tyrolite, CaCu₅(AsO₄)₂(CO₃)(OH) ₄.6H₂O, from Brixlegg, Tyrol, Austria, is reported. Comparison with copper hydroxy-arsenate and basic carbonates was used to achieve assignments of the observed bands. The AsO₄^3- group is characterized by two υ₄ modes around 433 and 480 cm^-1 plus a broad band around 840 cm^-1 as the υ overlapping with the υ. The υ₃ mode is observed as a single band around 355 cm ^-1. The CO₃^2- υ₁ mode is observed around 1035 and 1088 cm^-1, although this assignment is difficult because of the in-plane OH bending vibrations at similar frequencies. Two υ₄ modes are assigned to the 717 and 755 cm^-1 bands. The υ₃ mode is present as three bands at 1431, 1463, and 1498 cm^-1. A large split caused by bridging carbonates may explain the band at 1370 cm ^-1. The H₂O bending region shows two bands at 1635 and 1667 cm^-1 together with stretching modes around 3204 and 3303 cm^-1, the first associated with adsorbed H₂O, while the second indicates more strongly bonded H₂O. Three bands around 3534, 3438, and 3379 cm ^-1 are assigned to OH stretching modes of the OH groups in the crystal structure. The 202, 262, 301, 524, and 534 cm^-1 bands are assigned to Cu-OH bending and stretching modes, whereas the bands around 179, 202, and 217 cm^-1 are ascribed to O-(Ca, Cu)-O(H) with the O(H) at much greater distance from the cation. The bands around 503, 570, and 598 cm^-1 are ascribed to the Cu-O stretching modes. Index Headings: Arsenate; Carbonate; Hydroxyl groups; Raman microscopy; Tyrolite.

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