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Localized Orbital Studies of Hydrogen Bonding. II. Dimers Containing H 2 0, NH 3, HF, H 2 CO, and HCN
Journal of the American Chemical Society (1975)
  • Mark S. Gordon
  • Dennis E. Tallman
  • Cathy Monroe
  • Michael Steinbach
  • Jill Armbrust
Abstract

INDO localized molecular orbitals (LMO's) are utilized for investigating the nature of intermolecular hydrogen bonding in the fully geometry optimized dimers (HFh, (Hz0)2, (NH3)2, FH-OH2, HOH-FH, FH-NH3, H 2NH-FH, H20-HNH2, HOH-NH3, HCN-HF, and HzCO-HF. The results suggest that a reasonable measure of relative hydrogen bond strengths should be the intra bond, two-center, one-electron interference energy connecting the acceptor atom and donated proton. This approach views the net stabilization energy of a hydrogen bonded dimer as arising from a large energy decrease due to formation of the hydrogen bond, modified by smaller energy increases due to internal decreases in monomer bond energies upon formation of the dimer. Hydrogen bond stabilization app.ears to be closely related to the extent of charge transfer within the hydrogen bonded complex. The calculated transfer of charge can largely be explained in terms of electron density shifts within the acceptor lone pairs, while the decrease in electron density on the proton is discussed in terms of the donor XH bond. The approach presented should be particularly useful for analyzing intramolecular hydrogen bonding systems where the hydrogen bond energy is not simply obtainable from monomer-dimer energy differences.

Disciplines
Publication Date
March, 1975
Publisher Statement
Reprinted (adapted) with permission from Journal of the American Chemical Society 97 (1975): 1326, doi:10.1021/ja00839a007. Copyright 1975 American Chemical Society.
Citation Information
Mark S. Gordon, Dennis E. Tallman, Cathy Monroe, Michael Steinbach, et al.. "Localized Orbital Studies of Hydrogen Bonding. II. Dimers Containing H 2 0, NH 3, HF, H 2 CO, and HCN" Journal of the American Chemical Society Vol. 97 Iss. 6 (1975)
Available at: http://works.bepress.com/mark_gordon/18/