Photoelectron spectroscopic and density functional theoretical studies of the 2'-deoxycytidine homodimer radical anion.
J Chem Phys
; 139(7): 075101, 2013 Aug 21.
Article
em En
| MEDLINE
| ID: mdl-23968113
ABSTRACT
The intact (parent) 2'-deoxycytidine homodimer anion, (dC)2 (â-), was generated in the gas phase (in vacuo) using an infrared desorption∕photoemission source and its photoelectron spectrum was recorded using a pulsed, magnetic bottle photoelectron spectrometer. The photoelectron spectrum (PES) revealed a broad peak with the maximum at an electron binding energy between 1.6 and 1.9 eV and with a threshold at â¼1.2 eV. The relative energies and vertical detachment energies of possible anion radicals were calculated at the B3LYP/6-31++G(∗∗) level of theory. The most stable anion radicals are the complexes involving combinations of the sugar[middle dot][middle dot][middle dot]base and base[middle dot][middle dot][middle dot]base interactions. The calculated adiabatic electron affinities and vertical detachment energies of the most stable (dC)2 (â-) anions agree with the experimental values. In contrast with previous experimental-computational studies on the anionic complexes involving nucleobases with various proton-donors, the electron-induced proton transferred structures of (dC)2 (â-) are not responsible for the shape of PES.
Texto completo:
1
Base de dados:
MEDLINE
Assunto principal:
Teoria Quântica
/
Desoxicitidina
Idioma:
En
Revista:
J Chem Phys
Ano de publicação:
2013
Tipo de documento:
Article
País de afiliação:
Polônia