Primary kinetic isotope effects (KIE) have been determined spectrophotometrically for the reaction of NAD(+) analogues (pyridinium, quinolinium, phenanthridinium, and acridinium ions) with 1,3-dimethyl-2-phenylbenzimidazoline in a 4:1 mixture of 2-propanol and water by volume at 25 degreesC. The values of KIE varied systematically from 6.27 to 4.06 as the equilibrium constant changed from around 10 to around 10(12). This is consistent with Marcus theory of atom transfer, assuming that there are no high-energy intermediates. Within this theory, the perpendicular effect is responsible for most of the change in KIE. The Marcus theory of atom transfer is consistent with a linear, triatomic model of the reaction. Perpendicular effects arise from the systematic decrease of bond distances and increase of bond orders in the critical complexes of the two related degenerate hydride transfer reactions as their C-H bonds become stronger. The parallel effect (Leffler-Hammond effect) is attenuated by the fairly high intrinsic barrier (lambda /4 is around 92 kJ/mol) and makes a smaller contribution to the change in the KIE.