title: Base and phosphate electron detachment energies of deoxyribonucleotide anions.
abstract: Photoelectron spectra of deoxyribonucleotide anions are interpreted with ab initio, electron propagator calculations. Ground-state structures display hydrogen bonds which are not present in less stable minima that resemble Watson-Crick fragment geometries. For the adenosine and thymidine anions, there are two vertical electron detachment energies (VEDEs) within 0.1 eV of each other that correspond to phosphate- and base-centered Dyson orbitals (DOs). The first VEDE of the cytidine anion belongs to a phosphate-centered DO. The anomalously low VEDE of the guanosine anion is assigned to a base-centered, pi DO. Higher VEDEs of all four anions also are assigned.
authors.affiliation: Department of Chemistry, Kansas State University, Manhattan, KS 66506-3701, USA.
authors.forename: Viatcheslav V
authors.initials: VV
authors.lastname: Zakjevskii
authors.forename: Samuel J
authors.initials: SJ
authors.lastname: King
authors.forename: Olga
authors.initials: O
authors.lastname: Dolgounitcheva
authors.forename: Viatcheslav G
authors.initials: VG
authors.lastname: Zakrzewski
authors.forename: Joseph Vincent
authors.initials: JV
authors.lastname: Ortiz
mesh_terms: D000249:Adenosine Monophosphate / Q000737:chemistry; D000838:Anions / Q000737:chemistry*; D003568:Cytidine Monophosphate / Q000737:chemistry; D003854:Deoxyribonucleotides / Q000737:chemistry*; D004583:Electrons; D006157:Guanosine Monophosphate / Q000737:chemistry; D015394:Molecular Structure; D004364:Pharmaceutical Preparations; D010710:Phosphates / Q000737:chemistry*; D013816:Thermodynamics; D013938:Thymidine Monophosphate / Q000737:chemistry
chemical_list: D000838:Anions; D003854:Deoxyribonucleotides; D004364:Pharmaceutical Preparations; D010710:Phosphates; D013938:Thymidine Monophosphate; D000249:Adenosine Monophosphate; D006157:Guanosine Monophosphate; D003568:Cytidine Monophosphate