 Solution

Here $V(x)$ is potential energy, $E$ is the stationary-state total energy eigenvalue, and $\psi (x)$ is its spatial wavefunction. Wavefunction normalization gives $\int |\psi {|}^{2}dx=1$, and $|\psi {|}^{2}dx$ is the probability of finding the particle in $dx$.

A bound state requires $-V_0<E<0$. Inside the well the equation is ${\psi }^{\prime \prime }=-k^2\psi$, whereas outside it is ${\psi }^{\prime \prime }=q^2\psi$, withThe ground state is even and has no node, selecting $\cos (kx)$ inside. Normalizability selects decaying, not growing, exterior exponentials. Continuity of $\psi$ and ${\psi }^{\prime }$ givesThe first excited state, if present, is odd: a sine inside and opposite-sign decaying tails outside. Matching gives $-k_1\cot (k_{1}a/2)=q_1>0$. On its first odd branch, $\pi /2<k_{1}a/2<\pi$, hence $k_{1}a>\pi$. Since $k_1^2<2m{V}_0/{\hslash }^2$, existence requiresThis is the first odd bound-state threshold of a square well. There is no excited bound state below that threshold; equality gives a non-normalizable zero-energy limiting state, not an extra bound state.

For the numerical well,The exterior probability of a symmetric finite-well state includes both tails:The threshold is $9.40\mathrm{eV}$, exceeding the well depth, so there is no excited bound state. The rounded supplied coefficients integrate to $0.9973$ rather than exactly one; this rounding does not change the quoted probability precision materially.