Quantum Statistical Corrections to Dynamic Nuclear Magnetic Resonance

Abstract

A quantum statistical treatment of the chemical exchange between molecular eigenstates or conformations revealed previously unsuspected dynamic terms in the spin Hamiltonian operator that describes fast exchange. These terms resulted from the effect of nuclear spin on rotational and vibrational relaxation. With the traditional theory, an interpretation of new carbon-13 nuclear magnetic resonance measurements of the chemical shift of methylcyclohexane in solution showed fast-exchange equilibrium constants that were inconsistent with the slow-exchange free-energy difference and were spread over a range of 30 percent for the various carbon-13 positions. Modeling of the new terms indicated that they have the correct magnitude and temperature dependence to reconcile these inconsistencies.

Additional details