Used for estimating ground state energies

Take any normalized state ψ\ket{\psi}. Take it's Hamiltonian

H^=nEnϕnϕn\hat{H} = \sum_n E_n \ket{\phi_n}\bra{\phi_n} ψH^ψ=nEnψϕnϕnψ=nEnP(n)\braket{\psi | \hat{H} | \psi} = \sum_n E_n \braket{\psi|\phi_n}\braket{\phi_n|\psi} = \sum_n E_n\,P(n) nEnP(n)nE0P(n)=E0nP(n)=E0\sum_n E_n\,P(n) \geq \sum_n E_0\,P(n) = E_0 \sum_n P(n) = E_0 ψH^ψE0 normalized ψ\braket{\psi | \hat{H} | \psi} \geq E_0 \quad \forall\ \text{normalized } \ket{\psi}

But now you need to determine ground energy E0E_0

  1. Choose a family of trial states ψalpha\ket{\psi_alpha} parameterized by one or more params α\alpha.
  2. compute energy as function
E(α)=ψαH^ψαE(\alpha)=\bra{\psi_\alpha}\hat{H}\ket{\psi_\alpha}
  1. Minimize over α\alpha the best estimate is
Emin=minαE(α)E0E_\text{min} = \min_\alpha E(\alpha) \geq E_0

To reach the first excited state E1E_1 by restricting the trial state be ortho to the ground state

ϕ0ψα=0    ψαH^ψαE1\braket{\phi_0 | \psi_\alpha} = 0 \;\Rightarrow\; \braket{\psi_\alpha | \hat{H} | \psi_\alpha} \geq E_1

A trial state is a guess for the ground state that you build yourself with one or more free parameters baked in. e.g.,

ψα(x)=(2απ)1/4eαx2\psi_\alpha(x) = \left(\frac{2\alpha}{\pi}\right)^{1/4} e^{-\alpha x^2}

Example

Gaussian Trial State

These are some trial states

ψα(x)=Cαeα2x2,Cα=(2α2π)1/4\psi_\alpha(x) = C_\alpha\,e^{-\alpha^2 x^2}, \qquad C_\alpha = \left(\frac{2\alpha^2}{\pi}\right)^{1/4}

Using that trial state, prove KE

ψαp^22mψα=2α22m\braket{\psi_\alpha | \tfrac{\hat{p}^2}{2m} | \psi_\alpha} = \frac{\hbar^2\alpha^2}{2m}

Triangular Trial State

ψα(x)={Cα(1αx)x1/α0x>1/α,Cα=3α2\psi_\alpha(x) = \begin{cases} C_\alpha(1 - \alpha|x|) & |x| \leq 1/\alpha \\ 0 & |x| > 1/\alpha \end{cases}, \qquad C_\alpha = \sqrt{\frac{3\alpha}{2}} ddxx={0x<01x0\frac{d}{dx}|x| = \begin{cases}0&x<0\\1&x\geq 0\end{cases}

where sgn is the step function where delta is Dirac Delta

d2dx2x=2δ(x)\frac{d^2}{dx^2}|x| = 2\delta(x)

Prove KE

ψαp^22mψα=22mψα(x)d2dx2ψα(x)dx\braket{\psi_\alpha|\tfrac{\hat p^2}{2m}|\psi_\alpha} = -\frac{\hbar^2}{2m}\int_{-\infty}^{\infty}\psi_\alpha^*(x)\,\frac{d^2}{dx^2}\psi_\alpha(x)\,dx =22mψα(x)Cα(2αδ(x))dx= -\frac{\hbar^2}{2m}\int_{-\infty}^{\infty}\psi_\alpha^*(x)\,C_\alpha\big(-2\alpha\,\delta(x)\big)\,dx =22m2αCα2=22m2α3α2=32α22m= \frac{\hbar^2}{2m}\,2\alpha\,|C_\alpha|^2 = \frac{\hbar^2}{2m}\,2\alpha\cdot\frac{3\alpha}{2} = \frac{3\hbar^2\alpha^2}{2m}

Application

V(x)=12kx2,ω=kmV(x) = \tfrac{1}{2}kx^2, \qquad \omega = \sqrt{\frac{k}{m}} E0=12ωE_0 = \tfrac{1}{2}\hbar\omega

Gaussian Trial States

ψα=Cαeα2x2,Cα2=2α2π\psi_\alpha = C_\alpha e^{-\alpha^2 x^2}, \qquad C_\alpha^2 = \sqrt{\frac{2\alpha^2}{\pi}} V(x^)=ψα(x)2kx22dx=k8α2\braket{V(\hat x)} = \int_{-\infty}^{\infty}|\psi_\alpha(x)|^2\,\frac{kx^2}{2}\,dx = \frac{k}{8\alpha^2} x2=14α2\braket{x^2} = \frac{1}{4\alpha^2} E(α)=2α22m+k8α2E(\alpha) = \frac{\hbar^2\alpha^2}{2m} + \frac{k}{8\alpha^2}

Minimize

0=ddαE=2αmk4α30 = \frac{d}{d\alpha}E = \frac{\hbar^2\alpha}{m} - \frac{k}{4\alpha^3} 2αm=k4α3    α4=km42    α=(km42)1/4\frac{\hbar^2\alpha}{m} = \frac{k}{4\alpha^3} \;\Rightarrow\; \alpha^4 = \frac{km}{4\hbar^2} \;\Rightarrow\; \alpha = \left(\frac{km}{4\hbar^2}\right)^{1/4} minαE(α)=12km=12ω\min_\alpha E(\alpha) = \frac{1}{2}\hbar\sqrt{\frac{k}{m}} = \tfrac{1}{2}\hbar\omega

Triangular Trial States

V(x^)=kCα201/αx2(1αx)2dx=k20α2\braket{V(\hat x)} = k\,|C_\alpha|^2\int_{0}^{1/\alpha}x^2(1-\alpha x)^2\,dx = \frac{k}{20\alpha^2} E(α)=32α22m+k20α2E(\alpha) = \frac{3\hbar^2\alpha^2}{2m} + \frac{k}{20\alpha^2}

Minimize

α4=km302\alpha^4 = \frac{km}{30\hbar^2} minαE(α)=310ω0.548ω\min_\alpha E(\alpha) = \sqrt{\frac{3}{10}}\,\hbar\omega \approx 0.548\,\hbar\omega

Guesses

True ground is 0.5ω0.5\hbar \omega Gaussian estimate is 0.5ω0.5\hbar \omega Triangular estimate is 0.548ω0.548\hbar \omega