DFT Calculations of the Electron Affinities of Nucleic Acid Bases: Dealing with Negative Electron Affinities

摘要

To better understand the cause of the diversity in reported values of the electron affinities (EAs) for DNA bases, we performed a series of DFT (B3LYP functional) calculations at different basis set sizes. Through investigation of (1) trends in the values of EAs, (2) the excess electron spin distribution of the anion radical dependence on basis set size, (3) effect of the excess electron on ZPEs, we are able to identify the features of a basis set that allows for dipole-bound and continuum states to compete with molecular states for the electron. Smaller basis sets that confine the excess electron to the molecule allow for reasonable estimates of relative valence electron affinities excluding dipole-bound states and suggest the order of adiabatic valence electron affinities to be U ≈ T > C ≈ I (hypoxanthine) > A > G with G nearly 1 eV less electron affinic that U. Combining the best estimates from theory and experiment we place the adiabatic valence electron affinities of the pyrimidines as zero to +0.2 eV, whereas the purines A and G are predicted to be clearly negative with electron affinities of ca. -0.35 and -0.75 eV, respectively. The virtual states (i.e., negative electron affinities) for A and G in the gas-phase become relevant to biology when their energies are lowered to bound states in solvated systems. Indeed, our calculations performed including the effect of solvation (PCM model) show that all EAs for the DNA bases are positive and have the same relative order as found with the compact basis sets in the gas-phase calculations.