Electronic structure and spectroscopy of nucleic acid bases: Ionization energies, ionization-induced structural changes, and photoelectron spectra

K.B. Bravaya, O. Kostko, S. Dolgikh, A. Landau, M. Ahmed, and A.I. Krylov
J. Phys. Chem. A 114, 12305 – 12317 (2010)

We report high-level ab initio calculations and single-photon ionization mass spectrometry study of ionization of adenine (A), thymine (T), cytosine (C) and guanine (G). For thymine and adenine, only the lowest-energy tautomers were considered, whereas for cytosine and guanine we characterized five lowest-energy tautomeric forms. The first adiabatic and several vertical ionization energies (IEs) were computed using equation-of-motion coupled-cluster method for ionization potentials with single and double substitutions. Equilibrium structures of the cationic ground states were characterized by DFT with the wB97X-D functional. The ionization-induced geometry changes of the bases are consistent with the shapes of the corresponding molecular orbitals. For the lowest-energy tautomers, the magnitude of the structural relaxation decreases in the following series G>C>A>T, the respective relaxation energies being 0.41, 0.32, 0.25 and 0.20 eV. The computed adiabatic IEs (8.12, 8.93, 8.52-8.71 and 7.75-7.88 eV for A,T,C and G, respectively) agree well with the onsets of the photoionization efficiency (PIE) curves (8.20+/-0.05, 8.95+/-0.05, 8.60+/-0.05 and 7.75+/-0.05 eV). Vibrational progressions for the S0-D0 vibronic bands computed within double-harmonic approximation with Duschinsky rotations are compared with previously reported experimental photoelectron spectra.

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