期刊
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
卷 6, 期 3, 页码 705-717出版社
AMER CHEMICAL SOC
DOI: 10.1021/ct900515a
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The electronic structure of the three representative isomers of the ionized uracil dimers; is characterized by high-level electronic structure calculations. Noncovalent interactions between the fragments lower the vertical ionization energies by 0.13-0.35 eV, the largest drop being observed for the stacked and the T-shaped isomers. The initial hole is delocalized in the stacked and the H-bonded isomers and is localized in the T-shaped one. The ionization induces significant structural relaxation and increases the binding energies. The stacked dimer cation relaxes to the symmetric structure bound by 22.7 kcal/mol. The T-shaped dimer cation has a binding energy of 25.1 kcal/mol. Thus, the relative order of the stacked and T-shaped isomers is reversed upon ionization. Finally, the H-bonded isomer, which relaxes to the proton-transferred structure, is bound by 37.0 kcal/mol. The electronic spectra of all three isomers characterized at the vertical and the relaxed geometries show different patterns, which may be exploited in spectroscopic probing of ionization-induced dynamics in these species.
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