2.II.33B

Applications of Quantum Mechanics | Part II, 2005

Describe briefly the variational approach to the determination of an approximate ground state energy E0E_{0} of a Hamiltonian HH.

Let ∣ψ1⟩\left|\psi_{1}\right\rangle and ∣ψ2⟩\left|\psi_{2}\right\rangle be two states, and consider the trial state

∣ψ⟩=a1∣ψ1⟩+a2∣ψ2⟩|\psi\rangle=a_{1}\left|\psi_{1}\right\rangle+a_{2}\left|\psi_{2}\right\rangle

for real constants a1a_{1} and a2a_{2}. Given that

⟨ψ1∣ψ1⟩=⟨ψ2∣ψ2⟩=1,⟨ψ2∣ψ1⟩=⟨ψ1∣ψ2⟩=s,⟨ψ1∣H∣ψ1⟩=⟨ψ2∣H∣ψ2⟩=E,⟨ψ2∣H∣ψ1⟩=⟨ψ1∣H∣ψ2⟩=ϵ,\begin{aligned} \left\langle\psi_{1} \mid \psi_{1}\right\rangle &=\left\langle\psi_{2} \mid \psi_{2}\right\rangle=1, &\left\langle\psi_{2} \mid \psi_{1}\right\rangle=\left\langle\psi_{1} \mid \psi_{2}\right\rangle=s, \\ \left\langle\psi_{1}|H| \psi_{1}\right\rangle &=\left\langle\psi_{2}|H| \psi_{2}\right\rangle=\mathcal{E}, &\left\langle\psi_{2}|H| \psi_{1}\right\rangle=\left\langle\psi_{1}|H| \psi_{2}\right\rangle=\epsilon, \end{aligned}

and that ϵ<sE\epsilon<s \mathcal{E}, obtain an upper bound on E0E_{0} in terms of E,ϵ\mathcal{E}, \epsilon and ss.

The normalized ground-state wavefunction of the Hamiltonian

H1=p22m−Kδ(x),K>0,H_{1}=\frac{p^{2}}{2 m}-K \delta(x), \quad K>0,

ψ1(x)=λe−λ∣x∣,λ=mKℏ2.\psi_{1}(x)=\sqrt{\lambda} e^{-\lambda|x|}, \quad \lambda=\frac{m K}{\hbar^{2}} .

Verify that the ground state energy of H1H_{1} is

EB≡⟨ψ1∣H∣ψ1⟩=−12Kλ.E_{B} \equiv\left\langle\psi_{1}|H| \psi_{1}\right\rangle=-\frac{1}{2} K \lambda .

Now consider the Hamiltonian

H=p22m−Kδ(x)−Kδ(x−R)H=\frac{p^{2}}{2 m}-K \delta(x)-K \delta(x-R)

and let E0(R)E_{0}(R) be its ground-state energy as a function of RR. Assuming that

ψ2(x)=λe−λ∣x−R∣,\psi_{2}(x)=\sqrt{\lambda} e^{-\lambda|x-R|},

use (∗)(*) to compute s,Es, \mathcal{E} and ϵ\epsilon for ψ1\psi_{1} and ψ2\psi_{2} as given. Hence show that

E0(R)⩽EB[1+2e−λR(1+e−λR)1+(1+λR)e−λR]E_{0}(R) \leqslant E_{B}\left[1+2 \frac{e^{-\lambda R}\left(1+e^{-\lambda R}\right)}{1+(1+\lambda R) e^{-\lambda R}}\right]

Why should you expect this inequality to become an approximate equality for sufficiently large RR ? Describe briefly how this is relevant to molecular binding.

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