Past exam of the mathematics course of the University of Cambridge / 2005 / ii / Paper 2 / 33B / Solution

For a normalized trial state in the quadratic-form domain of a self-adjoint Hamiltonian operator bounded below, its expectation of $H$ is at least the ground energy $E_0$. Minimizing this Rayleigh quotient over a tractable trial family therefore supplies an upper bound.

For the two states, set $a_{\pm }=(a_1\pm a_2)/\sqrt{2}$. Their quotient isThe strict assumption $ϵ<sE$ excludes $|s|=1$, since equality in the overlap Cauchy-Schwarz bound would then force the two states to be proportional and $ϵ=sE$. Thus $|s|<1$. The two generalized eigenvalues are $(E\pm ϵ)/(1\pm s)$, and their difference has the sign of $ϵ-sE$. The symmetric trial is the lower one, so

For the single attractive delta well, the supplied wavefunction has norm one because $\int \lambda e^{-2\lambda |x|}dx=1$. Its kinetic energy in quadratic-form notation is ${\hslash }^2\int |{\psi }_1^{\prime }{|}^2/(2m)={\hslash }^2{\lambda }^2/(2m)$, and its delta potential energy is $-K|{\psi }_1(0){|}^2=-K\lambda$. With $\lambda =mK/{\hslash }^2$ this givesIts derivative jump is ${\psi }_1^{\prime }(0+)-{\psi }_1^{\prime }(0-)=-2\lambda {\psi }_1(0)$, exactly the delta boundary condition, so it is an eigenstate. A decaying bound state on the two half-lines must have a common decay rate fixed by this same jump; there is only this one negative-energy state, confirming it is the ground state.

For $R>0$, integrate the overlap on the three regions $x<0$, $0<x<R$, $x>R$. Put $a=\lambda R$. The result isThe second equality is the single-well energy plus the extra delta expectation; the third follows by applying either single-well eigenvalue equation in the cross matrix element. Moreover $ϵ-sE=K\lambda e^{-a}[(1+a)e^{-2a}-1]<0$, so the preceding bound applies. Substitution givesFor widely separated wells, each localized orbital is close to an isolated-well ground state and the low-energy subspace is accurately their span; the symmetric combination captures the leading tunneling energy lowering. In the limit both exact and trial energies approach $E_B$. This illustrates electronic molecular binding: sharing an orbital between attractive centers can lower its energy below the separated-center value. A full equilibrium bond length would also require the repulsion of the positive centers.