Atomic dipole approximation and energies of interactions between purine and pyrimidine bases. I. Electrostatic interactions of adenine with uracil, thymine, thiouracils, dihydrouracil, and 5‐fluorouracil

The atomic dipole approximation has been employed to calculate the energies of electrostatic interaction between adenine and various pyrimidine derivatives. Minima of the interaction energy for various planar configurations were determined. Inclusion of the “monopole–dipole” and “dipole–dipole” terms in the multipole expansion improves considerably the agreement with experimental data. The effect of sulfur substitution has been investigated in detail. Formation of NH…︁S hydrogen bonds is less favorable than of NH…︁O bonds, due largely to the lower atomic dipole of the sulfur atom resulting from the shift of the π‐electron charge toward the neighboring carbon. The results are relevant to the interactions of thiouracils in nucleic acids.