UV photoelectron and ab initio quantum mechanical characterization of nucleotides: The valence electronic structure of anionic 2′-deoxyadenosine-5′-phosphate

✍ Scribed by Nancy S. Kim; Qing Jiang; Pierre R. Lebreton

• Publisher: John Wiley and Sons
• Year: 1996
• Tongue: English
• Weight: 749 KB
• Volume: 60
• Category: Article
• ISSN: 0020-7608
• DOI: 10.1002/(sici)1097-461x(1996)60:8<1735::aid-qua2>3.0.co;2-z

✦ Synopsis

He(1) ultraviolet (W) photoelectron spectroscopy and ab initio, self-consistent field (SCF) calculations with the 6-31G basis set have been employed to characterize the valence electronic structures of anionic Z'-deoxyadenosine-5'-phosphate (5'-dAMP-). Theoretical ionization potentials (IPS) of 5'-dAMP-, of the neutral model compounds 9-methyladenine (9-MeA) and 3-hydroxytetrahydrofuran (3-OH-THF), and of the model anion CH,HPO, have been obtained by applying Koopmans' theorem to ab initio SCF results. The ionization potentials predicted from the SCF calculations have been compared to He(1) photoelectron spectra of 9-MeA and 3-OH-THF. The SCF calculations predict a value (8.45 eV), for the highest occupied rr orbital in 9-MeA which agrees well with the experimental vertical IP (8.39 eV). However, IPS for the highest occupied lone-pair orbitals in 3-OH-THF are predicted to be more than 1.52 eV higher than the experimental IPS. Results from recently reported [H.