UC San Diego

© The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2015. We reaffirm our conclusion that secondary deuterium isotope effects on acidity are due to n-σ∗ delocalization that decreases vibrational frequencies and zero-point energies. We reject an electrostatic or inductive explanation that arises from the anharmonicity of the C-H bond. We address calculated values of atomic charges, dipole moments, and dipole-moment derivatives dμ/dr, and we show the isotope effect to be a stereoelectronic phenomenon arising from harmonic vibrations.