Analysis of Proton NMR in Hydrogen Bonds in Terms of Lone-Pair and Bond Orbital Contributions.

NMR spectroscopic parameters of the proton involved in hydrogen bonding are studied theoretically. The set of molecules includes systems with internal resonance-assisted hydrogen bonds, internal hydrogen bonds but no resonance stabilization, the acetic acid dimer (AAD), a DNA base pair, and the hydrogen succinate anion (HSA). Ethanol and guanine represent reference molecules without hydrogen bonding.

The analysis of NMR J-couplings of saturated and unsaturated compounds by the localized second order polarization propagator approach method.

Calculations of NMR J-coupling with polarization propagators are not invariant under unitary transformations at second order level of approach, second order polarization propagator approach (SOPPA). They are only invariant at first order or random phase level of approach (RPA). We performed "localized" SOPPA (Loc-SOPPA), calculations of J-couplings applying two different schemes for the localization of molecular orbitals(LMO): Foster-Boys and Pipek-Mezey.