Past exam of the mathematics course of the University of Cambridge / 2001 / ib / Paper 1 / 18F (Quantum Mechanics)

Infinite walls impose the Dirichlet boundary conditions $\psi (-a)=\psi (a)=0$. Inside the infinite square well, the time-independent Schrödinger equation is $-{\hslash }^2{\psi }^{\prime \prime }/(2m)=E\psi$. Its nonzero solutions satisfying both endpoint conditions have wave numbers $k_n=n\pi /(2a)$, $n\ge 1$. Sincethe normalized energy eigenstates are the sine modes with prefactor $1/\sqrt{a}$. They are orthonormal by sine orthogonality and complete by the Fourier sine series on an interval of length $2a$. Differentiating twice gives

The initial wavefunction has unit norm, since ${\int }_0^a(2/a){\sin }^2(\pi x/a)dx=1$. On its nonzero half, $-{\hslash }^2{\psi }^{\prime \prime }/(2m)=E_{\ast }\psi$ with $E_{\ast }={\hslash }^2{\pi }^2/(2m{a}^2)$. A small domain qualification is important: the derivative jumps at zero, so the state is not in the operator domain of the Dirichlet Hamiltonian operator. Its finite energy expectation value is nevertheless defined by the quadratic form of a positive quantum Hamiltonian. The energy form of a half-well sine state givesThis is also the rigorous weak interpretation of the printed $\int \psi H\psi$. Indeed the distributional second derivative is ${\psi }^{\prime \prime }=-(\pi /a{)}^2\psi +\sqrt{2/a}(\pi /a){\delta }_0$ inside the well. The Dirac delta term pairs to zero because $\psi (0)=0$. One should not instead conclude that this state is an energy eigenstate from its equation on just the positive half.

Its coefficients in the full-well energy eigenstates areFor even $n$, sine orthogonality gives $a_2=-1/\sqrt{2}$ and all other even coefficients zero. For $n=2p+1$, set $u=x/a$ and use $\sin [n\pi (u+1)/2]=(-1{)}^p\cos (n\pi u/2)$. Product-to-sum integration then givesSince these coefficients are $O(n^{-2})$, ${\sum }_n{E}_n|a_n{|}^2$ converges, confirming that the state has finite energy. With $E_n=n^2{E}_1$, the spectral expression isThe kinetic-energy quadratic form equals this spectral sum: expanding the weak derivative in the corresponding orthonormal cosine modes and using Parseval's identity gives $\int |{\psi }^{\prime }{|}^2={\sum }_n{k}_n^2|a_n{|}^2$. Equating it to the directly integrated value $4E_1$ provesIn contrast, ${\sum }_n{E}_n^2|a_n{|}^2$ diverges, consistently showing why $H\psi$ is not an ordinary square-integrable vector even though the energy expectation is finite.