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Molecular orbital investigation of multiply hydrogen bonded systems. Formic acid dimer and DNA base pairs
Journal of the American Chemical Society
  • Steve Scheiner, Utah State University
  • C. W. Kern, Ohio State University
Document Type
Publication Date
American Chemical Society
Proton transfers within the formic acid dimer are studied using various methods. Minimum atomic basis sets yield single- and double-well potentials for single and double proton transfers, respectively, in agreement with extended basis set calculations. A potential energy surface for the decoupled proton transfers using the 4-3 IG basis set indicates that a simultaneous and synchronous motion of two protons is an adequate first approximation to the optimal mode of double transfer. All-electron PRDDO calculations are carried out for proton transfers within the base pairs guanine-cytosine and adenine-thymine. Single transfers are again found to be characterized by single-hell potentials and double transfers bl double-well potentials. Quantum mechanical tunneling rates and equilibrium constants are calculated for the most facile mode which involves a double proton transfer in the guanine-cytosine pair. The values obtained are compared to experimental data and inferences are drawn concerning the importance of the tunneling phenomenon in mutagenesis.
Originally published in the Journal of the American Chemical Society by the American Chemical Society . Publisher’s PDF available through remote link. DOI: 10.1021/ja00509a012
Citation Information
Molecular Orbital Study of Multiply Hydrogen Bonded Systems: Formic Acid Dimer and DNA Base Pairs S. Scheiner and C. W. Kern J. Am. Chem. Soc., 1979 101 (15), 4081-4085.