[Physics] Kinetic Energy in Maxwell-Boltzmann distribution

kinetic-theorystatistical mechanics

So I was trying to arrange the expression of a Maxwell-Boltzmann velocity vector distribution into a kinetic energy distribution. Since we know that $E= \frac{1}{2} mv^2$ we can rearrange this expression to give $v^2=\frac{2E}{m}$. If we insert this expression in a Maxwell-Boltzmann distribution:
$$f(v)=\left(\frac{m}{2\pi K_BT}\right)^\frac{3}{2} \exp\left(\frac{-m(v_x^2 + v_y^2 + v_z^2)}{2K_BT}\right)$$

we get:
$$f(E)=\left(\frac{m}{2\pi K_BT}\right)^\frac{3}{2} \exp\left(\frac{-E}{K_BT}\right)$$

But Wikipedia says that the kinetic energy distribution is:
$$f(E)=2\left(\frac{E}{\pi}\right)^\frac{1}{2}\left(\frac{1}{K_BT}\right)^\frac{3}{2} \exp\left(\frac{-E}{K_BT}\right)$$
What am I missing here?

Best Answer

Kinetic energy distribution $f_E(E)$ is a function that gives probability per unit energy interval.

Since kinetic energy $E$ is a function of speed, this distribution is related to speed distribution $f_v(v)$, but its value at any energy $E$ is not merely proportional to value of $f_v(v(E))$. The derivation of $f_E(E)$ from $f_v(v)$ relies on the substitution theorem from the integral calculus.

For positive speeds $v_1,v_2$ and corresponding energies $E_1=\frac{1}{2}mv_1^2, E_2=\frac{1}{2}mv_2^2$, the probability that particle has kinetic energy in the interval $(E_1,E_2)$ is the same as the probability that it has speed in the interval $(v_1,v_2)$. We transform the expression of the second probability in the following way:

$$ P = \int_{v_1}^{v_2}f_v(v)dv => (subst. theorem) => \int_{E_1}^{E_2}f_v(v(E))v'(E) dE $$ where

$$ v(E) = (2E/m)^{1/2} $$ and $v'(E)$ is derivative of this function at value $E$.

The expression of the first probability is

$$ P = \int_{E_1}^{E_2}f_E(E)dE. $$

Since we can choose $v_1,v_2$ arbitrarily close to each other, it must be

$$ f_E(E) = f_v(v(E))\frac{dv(E)}{dE}. $$

Substituting

$$ f_v(v) = \left(\frac{m}{2\pi k_BT}\right)^{3/2} 4\pi v^2 e^{-\frac{mv^2}{2k_B T}} $$

we obtain $$ f_E(E) = \left(\frac{m}{2\pi k_BT}\right)^{3/2} 4\pi 2E/m \cdot e^{-\frac{E}{k_B T}} \cdot (2/m)^{1/2}\frac{1}{2}E^{-1/2} $$

and after simplification $$ f_E(E) = \left(\frac{1}{\pi k_BT}\right)^{3/2} 2\pi \cdot E^{1/2} e^{-\frac{E}{k_B T}}. $$