Simulated Raman spectra of four tetraphenylbutadiene polymorphs

We report a combined experimental and theoretical investigation on the Raman spectra of the polymorphs α, β, γ, and δ of 1,1,4,4‐tetraphenyl‐1,3‐butadiene (TPB), in the region of the intramolecular modes. The interpretation of the polarized spectra is supported by ab‐initio calculations for the isolated molecules and by lattice dynamics calculations for the crystals. The calculations reproduce the peculiar, and surprisingly large, differences among the spectra of the various polymorphs. The phenyl groups of 1,1,4,4‐tetraphenyl‐1,3‐butadiene may arrange themselves around the butadiene skeleton in 2 stable conformers, which have either inversion (Ci) or 2‐fold (C2) symmetry and therefore exhibit intramolecular vibrations with quite different Raman selection rules and spectra. The compound forms 4 crystalline polymorphs (α, β, γ, and δ) with different combinations of Ci and C2 conformers, and correspondingly different intramolecular spectra. The theoretical calculations provide a quantitative analysis of the various spectra.