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UV photoelectron and ab initio quantum mechanical characterization of nucleotides: The valence electronic structure of anionic 2′‐deoxyadenosine‐5′‐phosphate
Author(s) -
Kim Nancy S.,
Jiang Qing,
Lebreton Pierre R.
Publication year - 1996
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/(sici)1097-461x(1996)60:8<1735::aid-qua2>3.0.co;2-z
Subject(s) - chemistry , ab initio , ab initio quantum chemistry methods , basis set , valence (chemistry) , ionization energy , electronic structure , valence electron , ion , x ray photoelectron spectroscopy , computational chemistry , ionization , configuration interaction , molecular orbital , lone pair , atomic physics , electron , molecule , density functional theory , nuclear magnetic resonance , physics , organic chemistry , quantum mechanics
He(I) ultraviolet (UV) 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 2′‐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 3 HPO 4 − 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(I) photoelectron spectra of 9‐MeA and 3‐OH‐THF. The SCF calculations predict a value (8.45 eV), for the highest occupied π 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. S. Kim and P. R. LeBreton, Proc. Natl. Sci. USA 91, 3725–3729 (1994), and N. S. Kim and P. R. LeBreton, J. Am. Chem. Soc., 118, 3694 (1996)] second‐order Møller‐Plesset perturbation (MP2) calculations and configuration interaction calculations using the configuration interaction singles (CIS) method indicate that configuration interaction effects strongly influence the energies of the first five ionization events arising from removal of electrons from the closed‐shell model anion CH 3 HPO 4 − . Results from the 6‐31G SCF calculations of 5′‐dAMP − , 9‐MeA, 3‐OH‐THF, and CH 3 HPO 4 − indicates that valence orbital electron distributions in the nucleotide and in the model compounds and anion are similar. The correspondence between the orbital structure of the nucleotide, and the model compounds and anion makes it possible, employing experimental photoelectron data and MP2/CIS computational results for the model compounds and anion, to individually correct IPs calculated for the nucleotide at the 6‐31G SCF level. Here, this approach has provided values for the 13 lowest IPs of 5′‐dAMP − and indicates that the first IPs of the base, sugar, and phosphate groups are 6.1, 7.8, and 5.5 eV, respectively. © 1996 John Wiley & Sons, Inc.