A new interstellar molecule, FeC (
We report relatively persistent, open‐shell thiophene‐based double helices, radical cations 1•+‐TMS12and 2•+‐TMS8. Closed‐shell neutral double helices, 1‐TMS12and 2‐TMS8, have nearly identical first oxidation potentials,
- NSF-PAR ID:
- 10446368
- Publisher / Repository:
- Wiley-Blackwell
- Date Published:
- Journal Name:
- Photochemistry and Photobiology
- Volume:
- 97
- Issue:
- 6
- ISSN:
- 0031-8655
- Page Range / eLocation ID:
- p. 1376-1390
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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Abstract X 3Δi ), has been identified in the circumstellar envelope of the carbon-rich asymptotic giant branch star IRC+10216. FeC is the second iron-bearing species conclusively observed in the interstellar medium, in addition to FeCN, also found in IRC+10216. TheJ = 4 → 3, 5 → 4, and 6 → 5 rotational transitions of this free radical near 160, 201, and 241 GHz, respectively, were detected in the lowest spin–orbit ladder, Ω = 3, using the Submillimeter Telescope of the Arizona Radio Observatory (ARO) for the 1 mm lines and the ARO 12 m at 2 mm. Because the ground state of FeC is inverted, these transitions are the lowest energy lines. The detected features exhibit slight U shapes with LSR velocities nearV LSR≈ −26 km s−1and linewidths of ΔV 1/2≈ 30 km s−1, line parameters characteristic of IRC+10216. Radiative transfer modeling of FeC suggests that the molecule has a shell distribution with peak radius near 300R *(∼6″) extending out to ∼500R *(∼10″) and a fractional abundance, relative to H2, off ∼ 6 × 10−11. The previous FeCN spectra were also modeled, yielding an abundance off ∼ 8 × 10−11in a larger shell situated near 800R *. These distributions suggest that FeC may be the precursor species for FeCN. Unlike cyanides and carbon-chain molecules, diatomic carbides with a metallic element are rare in IRC+10216, with FeC being the first such detection. -
null (Ed.)Of particular interest in radiation-induced charge transfer processes in DNA is the extent of hole localization immediately after ionization and subsequent relaxation. To address this, we considered double stranded oligomers containing guanine (G) and 8-oxoguanine (8OG), i.e. , ds(5′-GGG-3′) and ds(5′-G8OGG-3′) in B-DNA conformation. Using DFT, we calculated a variety of properties, viz. , vertical and adiabatic ionization potentials, spin density distributions in oxidized stacks, solvent and solute reorganization energies and one-electron oxidation potential ( E 0 ) in the aqueous phase. Calculations for the vertical state of the -GGG- cation radical showed that the spin was found mainly (67%) on the middle G. However, upon relaxation to the adiabatic -GGG- cation radical, the spin localized (96%) on the 5′-G, as observed in experiments. Hole localizations on the middle G and 3′-G were higher in energy by 0.5 kcal mol −1 and 0.4 kcal mol −1 , respectively, than that of 5′-G. In the -G8OGG- cation radical, the spin localized only on the 8OG in both vertical and adiabatic states. The calculated vertical ionization potentials of -GGG- and -G8OGG- stacks were found to be lower than that of the vertical ionization potential of a single G in DNA. The calculated E 0 values of -GGG- and -G8OGG- stacks are 1.15 and 0.90 V, respectively, which owing to stacking effects are substantially lower than the corresponding experimental E 0 values of their monomers (1.49 and 1.18 V, respectively). SOMO to HOMO level switching is observed in these oxidized stacks. Consequently, our calculations predict that local double oxidations in DNA will form triplet diradical states, which are especially significant for high LET radiations.more » « less
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