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What is the probability that two chemical species of binding energy $E$ will be bound?

Physics Asked by Joe Buckley on October 4, 2021

This may seem like a very simple question, but I’ve been agonising over it for days. What is the probability, $p$, that two chemical species with binding energy $E$, will be bound.

My first instinct is that
begin{equation} tag{1}label{1} p = Ae^{-beta E} end{equation}
with A some normalisation factor. This would give the correct behaviour ($pto1$ as $Eto -infty$ and $pto 0$ as $Eto 1$). But if this is the case, what is the form of $A$.

However, for
begin{equation}tag{2}label{2} p = 1 – e^{beta E} end{equation}
we see the same behaviour.

I have had a look in some literature for this, and have become even more confused, seeing both eqref{1} and eqref{2} used.

One Answer

The answer is not a simple function of binding energy E. What you need to know is the equilibrium constant $[AB]/[A][B]=K=exp (-beta {{G}_{0}})$, where ${{G}_{0}}$ denotes the free energy difference at reference concentrations. Doubling the concentration of unbound A & B will quadruple the concentration of bound AB.

K is proportional (not equal) to $exp (beta E)$ as you suspected, but there is a further factor that pertains to entropy. In gas phase, the entropy difference can be calculated via the semi-classical Sackur-Tetrode equation, which drags in Planck’s constant, cubed. The situation in liquid phase is not conceptually different, but solvation energies complicate things.

Answered by Bert Barrois on October 4, 2021

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