 Solution

Let $E=f_H(\psi )$. For any admissible variation $\eta$, differentiation with respect to a real parameter givesStationarity for all variations, including their imaginary multiples, forces $(H-E)\psi =0$; conversely this eigenvector equation makes the derivative vanish. Thus stationary Rayleigh quotients are exactly eigenvectors, with their eigenvalues as the quotient values.

Put $\kappa =e^2/(4\pi {ϵ}_0)$ and assume $\alpha >0$. The squared norm of the radial trial function is $4\pi {\int }_0^{\infty }{r}^2{e}^{-2\alpha r}dr=\pi /{\alpha }^3$. Its kinetic expectation, computed through $\int |\nabla \psi {|}^2$, is ${\hslash }^2{\alpha }^2/(2m)=\kappa a{\alpha }^2/2$. Splitting the potential integral at $R$ givesFor example, the first integral is $[1-e^{-2s}(1+2s+2s^2)]/(4{\alpha }^3)$ and the second is $e^{-2s}(R/(2\alpha )+1/(4{\alpha }^2))$, where $s=\alpha R$. ThereforeIts derivative is $\kappa [a\alpha -(1+2\alpha R)e^{-2\alpha R}]$. The actual stationary condition is consequentlyThe extra Coulomb factor in the printed stationary equation is an error: the common prefactor cancels on differentiation. The corrected equation is dimensionless on both sides. Its left side increases from zero, while its right side decreases from one, so it has one positive solution and gives the minimum in this trial family.

Let $\epsilon =R/a$ and $y=a\alpha$. Expansion of $(1+2s)e^{-2s}$ gives $1-2s^2+O(s^3)$. ThusThere is no linear correction in $R/a$. By the quantum variational principle, any normalized trial state gives an upper bound on the true ground energy. Choosing $\alpha =1/a$ already gives the exact boundIts small-radius expansion isUsing the optimized $\alpha$ improves this bound starting at order ${\epsilon }^4$, and hence gives the same leading finite-size correction. The true energy is also at least the point-nucleus value $-\kappa /(2a)$, since the finite-radius potential is nowhere more attractive.