An Equilibrium Deuterium Isotope Effect

A bonded hydrogen atom has about 1.4 times as much minimum vibrational energy as a similarly bonded deuterium atom.

This number is the square root of the mass ratio of 2.
For the 12C and 13C isotopes of carbon the vibrational energy of the lighter isotope is only about sqrt(13/12) = 1.04 times as large as that of the heavier isotope. Thus isotope effects are more much dramatic for D than for 13C.

The value of the minimum vibrational energy (zero point energy, zpe) depends on how tightly the atom is held. For a typical C-H bond the zpe is about 4 kcal/mole and that of C-D about 4 / 1.4 = 2.9 kcal/mole). The difference of about 1.1 kcal/mole would be larger for a more tightly bonded H and less for a more weakly bonded H.

Consider the hydride-shift equilibrium between isomers of the cation made by adding a proton to deuterated 2,3-dimethyl-2-butene:

The same stabilization of the C-H sigma electrons by the low LUMO of the neighboring carbon cation that makes the hydride shift easy, weakens the C-H bonds to all "b" hydrogens whose C-H bonds overlap with the vacant orbital on C.

For the cation isomer on the left of the equilibrium there are 6 C-D bonds of normal strength (not overlapping the LUMO of the cationic carbon) and 7 C-H bonds that are more or less weakened by "hyperconjugation" (depending on how conformation influences overlap).

For the cation isomer on the right of the equilibrium there are 6 C-H bonds of normal strength (not overlapping the LUMO of the cationic carbon) and 6 C-D bonds (plus one C-H bond) that are weakened by "hyperconjugation."

The zpe on the left is whatever it would be for the fully-deuterated version of the cation, plus 40% of the value for the seven weakened bonds in which D is replaced by H.

The zpe on the right is whatever it would be for the fully-deuterated version of the cation, plus 40% of the value for the one weakened bonds in which D is replaced by H and 40% of the value for the 6 normal bonds in which D is replaced by H.

Obviously the molecule on the right will be higher in energy by 40% of the difference in zpe between the 6 strong bonds and the 6 hyperconjugatively weakened bonds.

In 1990 Saunders and Cline measured this equilibrium constant and found that the molecule on the left was favored by a factor of 4.1 at 135 K and by 2.6 at 189 K. They used this to calculate an energy advantage of 420 cal/mole (not kcal/mole) for the molecle on the left, or about 70 cal/mole for each of the six H atoms to be in the less tightly bonded location.

This equilibrium isotope effect is only 0.070/1.100 ~ 7% as large as the effect observed when a bond to C-H (or C-D) is broken during the rate-determining step of an elimination reaction.