We present an investigation of small-scale structure in the distribution of large molecules/dust in the interstellar medium through observations of diffuse interstellar bands (DIBs). High signal-to-noise optical spectra were recorded toward the stars ρ Oph A, B, C, and DE using the University College London Echelle Spectrograph on the Anglo-Australian Telescope. The strengths of some of the DIBs are found to differ by about 5%-9% between the close binary stars ρ Oph A and B, which are separated by a projected distance on the sky of only c. 344 AU. This is the first star system in which such small-scale DIB strength variations have been reported. The observed variations are attributed to differences between a combination of carrier abundance and the physical conditions present along each sightline. The sightline toward ρ Oph C contains relatively dense, molecule-rich material and has the strongest λλ5850 and 4726 DIBs. The gas toward DE is more diffuse and is found to exhibit weak "C2" (blue) DIBs and strong yellow/red DIBs. The differences in diffuse band strengths between lines of sight are, in some cases, significantly greater in magnitude than the corresponding variations among atomic and diatomic species, indicating that the DIBs can be sensitive tracers of interstellar cloud conditions.

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