Abstract
We investigated the cryptic red chromophore, accompanying the blue S3˙- radical in ultramarine pigments, which usually was tentatively assigned to an unspecified isomer of either neutral S4 or ionic S4˙- species. To reveal its identity, we performed the first systematic density functional studies on periodic and large cluster models of red ultramarines, considering several S4/S4˙- isomers embedded in aluminosilicate cages. For both neutral and charged tetrasulfides the most stable confined isomer is the planar C2v one. The only plausible candidate for the red chromophore among the tetrasulfur species is the planar C2v isomer of the neutral S4 molecule, which, apart from being thermodynamically preferable, strongly absorbs green light and its vibrational modes match very well with the available Raman data. The C2v-S4˙- radical, if present at all in red ultramarines, could be identified by strong absorption in the near infrared region and possibly by the slightly larger isotropic value of the g tensor than that of the S3˙- radical.
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