Electron propagator and coupled-cluster calculations on the photoelectron spectra of thiouracil and dithiouracil anions.

O Dolgounitcheva, V G Zakrzewski, J V Ortiz

Index: J. Chem. Phys. 134(7) , 074305, (2011)

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Abstract

Electron affinities, vertical electron detachment energies, and isomerization energies of 4-thiouracil, 2-thiouracil, and 2,4-dithiouracil and their valence anions have been calculated with ab initio electron propagator and other many-body methods. Anions in which protons have been transferred to the C5 from the N1 or N3 ring positions have been considered, but the canonical forms are most stable for the 4-thiouracil and 2,4-dithiouracil anions. Electron affinities of 0.61, 0.26, and 0.87 eV have been determined for 4-thiouracil, 2-thiouracil, and 2,4-dithiouracil, respectively. Electron propagator calculations on the canonical anions yield vertical electron detachment energies that are in close agreement with experimental peaks at 1.05, 3.21, and 3.32 eV for 4-thiouracil and at 1.4 eV for 2,4-dithiouracil.