# Tunneling in chemical reactions

We know that quantum tunneling is the reason behind several natural phenomenon like alpha decay and thermonuclear fusion inside the stars. How can it influence chemical reactions by tunnelling a species through the activation energy? If so how does it influence the kinetics and fraction of molecules taking part in the reaction.

• Bit of a broad question. Relevant recent article: pubs.acs.org/doi/abs/10.1021/jacs.7b06035 Jul 2, 2018 at 17:25
• It is not a broad question. I just wanted to know the influence of tunneling on a chemical reaction and it's parameters. Jul 2, 2018 at 17:26
• Jul 2, 2018 at 17:27
• @orthocresol thanks for the article but I'm unable to access the complete article Jul 2, 2018 at 17:33
• Random primer: princeton.edu/chemistry/macmillan/group-meetings/…
– Zhe
Jul 2, 2018 at 17:44

The probability of tunnelling at an energy $E$ is given by $p(E)\approx e^{-bA\sqrt{m}}$ where $A$ is proportional to the area of the potential energy barrier above energy $E$, i.e. the top part of the potential barrier, $m$ the mass and $b$ some constants, $\pi, \hbar$. etc. Thus for a given mass and energy if the barrier is narrow, so $A$ is small, tunnelling is more likely than if the barrier is wide. At a given energy for the same barrier if the mass is large tunnelling is small. Thus we tend to see tunnelling only with H and D and not Cl atoms for example. Tunnelling is also important in electron transfer reactions.
As there is not just a single energy in a reaction but a distribution of energies, according to the Boltzmann distribution, it is necessary to modify the expression above to average over the energy but the basic result is the same, which is that the reaction rate constant is reduced by the factor $p(E)$.
[If the potential energy barrier is $V(x)$ then $\displaystyle p(E)=\exp\left(-\frac{2\sqrt{m}}{\hbar}\int_{x_1}^{x_2}\sqrt{V(x)-E}\right)$ where $x_{1,2}$ are the points either side of the barrier with energy $E$.]