 Solution

The $3d$ and $4s$ atomic orbitals of chromium are close enough in energy that electron-electron terms can overturn the simple filling order. The configuration $[\mathrm{Ar}]3d^{5}4s^1$ permits five singly occupied $3d$ orbitals and a parallel-spin $4s$ electron. Relative to $3d^{4}4s^2$, it removes the $4s$ pair and permits more parallel-spin exchange interactions, lowering the Coulomb-and-exchange contribution enough to offset the orbital promotion cost.

As qualitative bookkeeping, six parallel electron spins give $\left(\genfrac{}{}{0ex}{}{6}{2}\right)=15$ same-spin pairs, compared with $\left(\genfrac{}{}{0ex}{}{5}{2}\right)=10$ in high-spin $3d^{4}4s^2$. The individual exchange integrals are unequal, so this is an explanation of the tendency, rather than a quantitative atomic energy calculation. The observed ground state configuration is $\boxed{[\mathrm{Ar}]3d^{5}4s^1}$.^[ref]