The dimerisation of tribromoacetaldehyde in CCl4 and C6D12 solutions was investigated using Raman spectroscopy and different techniques of multivariate analysis. The m(C-H) stretching vibration band in dimers was blue shifted by 14/15 cm(-1), whereas the nu(C=O) dimer band was red-shifted by 7/8 cm(-1) in CCl4/C6D12 solutions versus their positions in monomers. The observed shifts were accompanied by a strong change in the bandwidth. The formation of dimers was confirmed by multivariate analysis of the Raman spectra of bromal recorded as a function of temperature. Structural and spectral information for (Br3CCHO)(2) dimers were obtained from calculations at the B3LYP/6-311++G(3df,3pd) level. (C) 2011 Elsevier B.V. All rights reserved.