Electronic spectroscopy of FUV-irradiated diamondoids: A combined experimental and theoretical study

Details Electronic spectroscopy of FUV-irradiated diamondoids: A combined experimental and theoretical study Electronic spectroscopy of FUV-irradiated diamondoids: A combined experimental and theoretical study

2011-01-21

arxiv.org/abs/1101.4146v4

Astrophys.J.729:91,2011

Physics

Chemical Physics

11 pages, 9 figures; published in The Astrophysical Journal; corrected minor mistakes compared to the published paper

Scientific paper

10.1088/0004-637X/729/2/91

Irradiation with high energy photons (10.2 - 11.8 eV) was applied to small diamondoids isolated in solid rare gas matrices at low temperature. The photoproducts were traced via UV absorption spectroscopy. We found that upon ionization the smallest of these species lose a peripheral H atom to form a stable closed-shell cation. This process is also likely to occur under astrophysical conditions for gas phase diamondoids and it opens the possibility to detect diamond-like molecules using their rotational spectrum since the dehydrogenated cations possess strong permanent dipole moments. The lowest-energy electronic features of these species in the UV were found to be rather broad, shifting to longer wavelengths with increasing molecular size. Calculations using time-dependent density functional theory support our experimental findings and extend the absorption curves further into the vacuum ultraviolet. The complete sigma - sigma* spectrum displays surprisingly strong similarities to meteoritic nanodiamonds containing 50 times more C atoms.

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