Intermolecular proton transfer induced by excess electron attachment to adenine(formic acid)n (n = 2, 3) hydrogen-bonded complexes

Journal Article · Thu Dec 06 04:00:00 EST 2007 · Chemical Physics, 342(1-3):215-222

DOI:https://doi.org/10.1016/j.chemphys.2007.10.005· OSTI ID:959218

Mazurkiewicz, Kamil; Haranczyk, Maciej; Storoniak, Piotr; Gutowski, Maciej S; Rak, Janusz; Radisic, Dunja; Eustis, Soren; Wang, Di; Bowen, Kit H

The research described in this product was performed in part in the Environmental Molecular Sciences Laboratory, a national scientific user facility sponsored by the Department of Energy's Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory. The propensity of the neutral complexes between both adenine and 9-methyladenine (A/MA) with formic acid (FA) in 1:2 and 1:3 stoichiometries to bind an excess electron was studied using photoelectron spectroscopy and quantum chemistry computational methods. Although an isolated canonical adenine does not support bound valence anions, solvation by one formic acid molecule stabilizes the excess electron on adenine. The adiabatic electron affinities of the A/MA(FA)2,3 complexes span a range of 0.8–1.23 eV indicating that the anions of 1:2 and 1:3 stoichiometries are substantially more stable than the anionic A–FA dimer (EA = 0.67 eV), which we studied previously and an attachment of electron triggers double-BFPT, confirmed at the MPW1K level of theory, in all the considered systems. Hence, the simultaneous involvement of several molecules capable of forming cyclic hydrogen bonds with adenine remarkably increases its ability to bind an excess electron. The calculated vertical detachment energies for the most stable anions correspond well with those obtained using photoelectron spectroscopy. The possible biological significance of our findings is briefly discussed.

• Research Organization: Pacific Northwest National Laboratory (PNNL), Richland, WA (US), Environmental Molecular Sciences Laboratory (EMSL)
• Sponsoring Organization: USDOE
• DOE Contract Number: AC05-76RL01830
• OSTI ID: 959218
• Journal Information: Chemical Physics, 342(1-3):215-222, Journal Name: Chemical Physics, 342(1-3):215-222 Journal Issue: 1-3 Vol. 342; ISSN CMPHC2; ISSN 0301-0104
• Country of Publication: United States
• Language: English

Related Subjects

08 HYDROGEN
ADENINES
ANIONS
CHEMISTRY
DIMERS
ELECTRON ATTACHMENT
ELECTRONS
Environmental Molecular Sciences Laboratory
FORMIC ACID
HYDROGEN
PHOTOELECTRON SPECTROSCOPY
PROTONS
SOLVATION
VALENCE