Complementary DNA base interactions: Application of recently refined electrostatic interaction theory

Abstract
Electrostatic interactions between the DNA bases in the Watson‐Crick hydrogen bonding configuration are examined in both the molecular and the atomic multipole representation using three different methods of calculation: (a) CNDO wave functions and definitions of moments, (b) IEHT wave functions and division of two‐center densities and (c) IHET wave functions with equally divided overlap densities. It is shown that the inclusion in the interaction series of terms at least as high as the quadrupole‐quadrupole is required to quantitatively characterize the interactions. Convergence is more rapid with the atomic multipole representation and is unaffected by the type of assignment of formal charges. A quantitative approach to the problem of the role of electrostatic interactions in hydrogen bonding in DNA is thus provided, with obvious impact on the investigation of molecular recognition processes.