Low-energy-barrier proton transfer induced by electron attachment to the guanine...cytosine base pair

Chemphyschem : a European Journal of Chemical Physics and Physical Chemistry
Anna SzyperskaKit H Bowen

Abstract

The photoelectron spectrum of the anion of the guanine...cytosine base pair (GC)(*-) is recorded for the first time. The observed variation in the spectral peak-height ratios with the source conditions suggests the presence of two or more anionic isomers. Two maxima of the broad bands in the photoelectron spectrum were measured at about 1.9 and about 2.6 eV. These values are very well reproduced by the vertical detachment energies of the B3LYP/6-31++G(d,p) calculated low-energy anionic structures, which are 1) the Watson-Crick base-pair anion with proton transferred from N1 of guanine to N3 of cytosine, 2) its analogue in which the proton is transferred from N9 of guanine to N7 of guanine, and 3) the global minimum geometry, which is formed from the latter anion by rotation of guanine about the axis approximately defined by C2 of guanine and C4 of cytosine. Furthermore, a minor difference in the stabilities of the two lowest energy anions explains the experimentally observed source (temperature) dependence of the PES spectrum. A rational procedure, based on the chemistry involved in the formation of anionic dimers, which enables the low-energy anions populated in the photoelectron spectrum to be identified is proposed. In contr...Continue Reading

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Citations

May 7, 2013·The Journal of Physical Chemistry. a·Adam S ChatterleyJan R R Verlet
Mar 26, 2010·Physical Chemistry Chemical Physics : PCCP·Yeon Jae KoKit H Bowen
Feb 11, 2014·Journal of Chemical Theory and Computation·Jiande GuHenry F Schaefer
Apr 26, 2012·The Journal of Physical Chemistry. B·Ashutosh GuptaHenry F Schaefer
Nov 13, 2012·The Journal of Physical Chemistry. B·Piotr StoroniakKit H Bowen
Sep 4, 2015·Physical Chemistry Chemical Physics : PCCP·Yi WangNathan I Hammer
May 14, 2016·The Journal of Physical Chemistry. B·Piotr StoroniakKit H Bowen
Apr 30, 2017·Chemical Science·Mamoru Fujitsuka, Tetsuro Majima
Jun 5, 2015·The Journal of Physical Chemistry. B·Shih-Hsun LinTetsuro Majima

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