degenerate perturbation

PHY1520H Graduate Quantum Mechanics. Lecture 22: Van der Wall potential and Stark effect. Taught by Prof. Arun Paramekanti

December 10, 2015 phy1520 No comments , , ,

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Disclaimer

Peeter’s lecture notes from class. These may be incoherent and rough.

These are notes for the UofT course PHY1520, Graduate Quantum Mechanics, taught by Prof. Paramekanti, covering [1] ch. 5 content.

Another approach (for last time?)

Imagine we perturb a potential, say a harmonic oscillator with an electric field

\begin{equation}\label{eqn:qmLecture22:20}
V_0(x) = \inv{2} k x^2
\end{equation}
\begin{equation}\label{eqn:qmLecture22:40}
V(x) = \mathcal{E} e x
\end{equation}

After minimizing the energy, using \( \PDi{x}{V} = 0 \), we get

\begin{equation}\label{eqn:qmLecture22:60}
\inv{2} k x^2 + \mathcal{E} e x \rightarrow k x^\conj = – e \mathcal{E}
\end{equation}

\begin{equation}\label{eqn:qmLecture22:80}
p^\conj = -e x^\conj = – \frac{e^2 \mathcal{E}}{k}
\end{equation}

For such a system the polarizability is

\begin{equation}\label{eqn:qmLecture22:100}
\alpha = \frac{e^2 }{k}
\end{equation}

\begin{equation}\label{eqn:qmLecture22:120}
\begin{aligned}
\inv{2} k \lr{ -\frac{ e \mathcal{E}}{k} }^2 + \mathcal{E} e \lr{ – \frac{e \mathcal{E}}{k} }
&= – \inv{2} \lr{ \frac{e^2}{k} } \mathcal{E}^2 \\
&= – \inv{2} \alpha \mathcal{E}^2
\end{aligned}
\end{equation}

Van der Wall potential

\begin{equation}\label{eqn:qmLecture22:140}
H_0 =
H_{0 1} + H_{0 2},
\end{equation}

where

\begin{equation}\label{eqn:qmLecture22:160}
H_{0 \alpha} = \frac{p_\alpha^2}{2m} – \frac{e^2}{4 \pi \epsilon_0 \Abs{ \Br_\alpha – \BR_\alpha} }, \qquad \alpha = 1,2
\end{equation}

The full interaction potential is

\begin{equation}\label{eqn:qmLecture22:180}
V =
\frac{e^2}{4 \pi \epsilon_0} \lr{
\inv{\Abs{\BR_1 – \BR_2}}
+
\inv{\Abs{\Br_1 – \Br_2}}

\inv{\Abs{\Br_1 – \BR_2}}

\inv{\Abs{\Br_2 – \BR_1}}
}
\end{equation}

Let

\begin{equation}\label{eqn:qmLecture22:200}
\Bx_\alpha = \Br_\alpha – \BR_\alpha,
\end{equation}

\begin{equation}\label{eqn:qmLecture22:220}
\BR = \BR_1 – \BR_2,
\end{equation}

as sketched in fig. 1.

fig. 1.  Two atom interaction.

fig. 1. Two atom interaction.

\begin{equation}\label{eqn:qmLecture22:240}
H_{0 \alpha}
=
\frac{\Bp^2}{2m}
-\frac{e^2}{4 \pi \epsilon_0 \Abs{\Bx_\alpha}}
\end{equation}

which allows the total interaction potential to be written
\begin{equation}\label{eqn:qmLecture22:260}
V =
\frac{e^2}{4 \pi \epsilon_0 R}
\lr{
1
+
\frac{R}{\Abs{\Bx_1 – \Bx_2 + \BR}}

\frac{R}{\Abs{\Bx_1 + \BR}}

\frac{R}{\Abs{-\Bx_2 + \BR}}
}
\end{equation}

For \( R \gg x_1, x_2 \), this interaction potential, after a multipole expansion, is approximately

\begin{equation}\label{eqn:qmLecture22:280}
V =
\frac{e^2}{4 \pi \epsilon_0} \lr{
\frac{\Bx_1 \cdot \Bx_2}{\Abs{\BR}^3}
-3 \frac{
(\Bx_1 \cdot \BR)
(\Bx_2 \cdot \BR)
}{\Abs{\BR}^5}
}
\end{equation}

1. \( O(\lambda) \)

.

With

\begin{equation}\label{eqn:qmLecture22:300}
\psi_0 = \ket{ 1s, 1s }
\end{equation}

\begin{equation}\label{eqn:qmLecture22:320}
\Delta E^{(1)} = \bra{\psi_0} V \ket{\psi_0}
\end{equation}

The two particle wave functions are of the form

\begin{equation}\label{eqn:qmLecture22:340}
\braket{ \Bx_1, \Bx_2 }{\psi_0} =
\psi_{1s}(\Bx_1)
\psi_{1s}(\Bx_2),
\end{equation}

so braket integrals must be evaluated over a six-fold space. Recall that

\begin{equation}\label{eqn:qmLecture22:740}
\psi_{1s} = \inv{\sqrt{\pi} a_0^{3/2} } e^{-r/a_0},
\end{equation}

so

\begin{equation}\label{eqn:qmLecture22:760}
\bra{\psi_{1s}} x_i \ket{\psi_{1s}}
\propto
\int_0^\pi \sin\theta d\theta \int_0^{2\pi} d\phi x_i
\end{equation}

where
\begin{equation}\label{eqn:qmLecture22:780}
x_i \in \setlr{ r \sin\theta \cos\phi, r \sin\theta \sin\phi, r \cos\theta }.
\end{equation}

The \( x, y \) integrals are zero because of the \( \phi \) integral, and the \( z \) integral is proportional to \( \int_0^\pi \sin(2 \theta) d\theta \), which is also zero. This leads to zero averages

\begin{equation}\label{eqn:qmLecture22:360}
\expectation{\Bx_1} = 0 = \expectation{\Bx_2}
\end{equation}

so

\begin{equation}\label{eqn:qmLecture22:380}
\Delta E^{(1)} = 0.
\end{equation}

2. \( O(\lambda^2) \)

.

\begin{equation}\label{eqn:qmLecture22:400}
\begin{aligned}
\Delta E^{(2)}
&= \sum_{n \ne 0} \frac{ \Abs{ \bra{\psi_n } V \ket{\psi_0} }^2 }{E_0 – E_n} \\
&= \sum_{n \ne 0} \frac{ \bra{\psi_0 } V \ket{\psi_n} \bra{\psi_n } V \ket{\psi_0} }{E_0 – E_n}.
\end{aligned}
\end{equation}

This is a sum over all excited states. We expect that this will be of the form

\begin{equation}\label{eqn:qmLecture22:420}
\Delta E^{(2)} = – \lr{ \frac{e^2}{4 \pi \epsilon_0} }^2 \frac{C_6}{R^6}
\end{equation}

\( \Bx_1 \) and \( \Bx_2 \) are dipole operators. The first time this has a non-zero expectation is when we go from the 1s to the 2p states (both 1s and 2s states are spherically symmetric).

Noting that \( E_n = -e^2/2 n^2 a_0 \), we can compute a minimum bound for the energy denominator

\begin{equation}\label{eqn:qmLecture22:440}
\begin{aligned}
\lr{E_n – E_0}^{\mathrm{min}}
&= 2 \lr{ E_{2p} – E_{1s} } \\
&= 2 E_{1s} \lr{ \inv{4} – 1 } \\
&= 2 \frac{3}{4} \Abs{E_{1s}} \\
&= \frac{3}{2} \Abs{E_{1s}}.
\end{aligned}
\end{equation}

Note that the factor of two above comes from summing over the energies for both electrons. This gives us

\begin{equation}\label{eqn:qmLecture22:460}
C_6
=
\frac{3}{2} \Abs{E_{1s}}
\bra{\psi_0 } \tilde{V} \ket{\psi_0},
\end{equation}

where

\begin{equation}\label{eqn:qmLecture22:480}
\tilde{V} =
\lr{
\Bx_1 \cdot \Bx_2
-3
(\Bx_1 \cdot \Rcap)
(\Bx_2 \cdot \Rcap)
}
\end{equation}

What about degeneracy?

\begin{equation}\label{eqn:qmLecture22:500}
\Delta E^{(2)}_n
= \sum_{m \ne n} \frac{ \Abs{ \bra{\psi_n } V \ket{\psi_0} }^2 }{E_0 – E_n}
\end{equation}

If \( \bra{\psi_n} V \ket{\psi_m} \propto \delta_{n m} \) then it’s okay.
In general the we can’t expect the matrix element will be anything but fully populated, say

\begin{equation}\label{eqn:qmLecture22:520}
V =
\begin{bmatrix}
V_{11} & V_{12} & V_{13} & V_{14} \\
V_{21} & V_{22} & V_{23} & V_{24} \\
V_{31} & V_{32} & V_{33} & V_{34} \\
V_{41} & V_{42} & V_{43} & V_{44} \\
\end{bmatrix},
\end{equation}

If we choose a basis so that

\begin{equation}\label{eqn:qmLecture22:540}
V =
\begin{bmatrix}
V_{11} & & & \\
& V_{22} & & \\
& & V_{33} & \\
& & & V_{44} \\
\end{bmatrix}.
\end{equation}

When this is the case, we have no mixing of elements in the sum of \ref{eqn:qmLecture22:500}

Degeneracy in the Stark effect

\begin{equation}\label{eqn:qmLecture22:560}
H = H_0 + e \mathcal{E} z,
\end{equation}

where

\begin{equation}\label{eqn:qmLecture22:580}
H_0 = \frac{\Bp^2}{2m} – \frac{e}{4 \pi \epsilon_0} \inv{\Abs{\Bx}}
\end{equation}

Consider the states \( 2s, 2 p_x, 2p_y, 2p_z \), for which \( E_n^{(0)} \equiv E_{2 s} \), as sketched in fig. 2.

fig. 2.  2s 2p degeneracy.

fig. 2. 2s 2p degeneracy.

Because of spherical symmetry

\begin{equation}\label{eqn:qmLecture22:600}
\begin{aligned}
\bra{2 s} e \mathcal{E} z \ket{ 2 s} &= 0 \\
\bra{2 p_x} e \mathcal{E} z \ket{ 2 p_x} &= 0 \\
\bra{2 p_y} e \mathcal{E} z \ket{ 2 p_y} &= 0 \\
\bra{2 p_z} e \mathcal{E} z \ket{ 2 p_z} &= 0 \\
\end{aligned}
\end{equation}

Looking at odd and even properties, it turns out that the only off-diagonal matrix element is

\begin{equation}\label{eqn:qmLecture22:620}
\bra{2 s} e \mathcal{E} z \ket{ 2 p_z } = V_1 = -3 e \mathcal{E} a_0.
\end{equation}

With a \( \setlr{ 2s, 2p_x, 2p_y, 2p_z } \) basis the potential matrix is

\begin{equation}\label{eqn:qmLecture22:640}
\begin{bmatrix}
0 & 0 & 0 & V_1 \\
0 & 0 & 0 & 0 \\
0 & 0 & 0 & 0 \\
V_1^\conj & 0 & 0 & 0 \\
\end{bmatrix}
\end{equation}

\begin{equation}\label{eqn:qmLecture22:660}
\begin{bmatrix}
0 & -\Abs{V_1} \\
-\Abs{V_1} & 0 \\
\end{bmatrix}
\end{equation}

implies that the energy splitting goes as

\begin{equation}\label{eqn:qmLecture22:680}
E_{2s} \rightarrow
E_{2s} \pm \Abs{V_1},
\end{equation}

as sketched in fig. 3.

fig. 3.  Stark effect energy level splitting.

fig. 3. Stark effect energy level splitting.

The diagonalizing states corresponding to eigenvalues \( \pm 3 a_0 \mathcal{E} \), are \( (\ket{2s} \mp \ket{2p_z})/\sqrt{2} \).

The matrix element above is calculated explicitly in lecture22Integrals.nb.

The degeneracy that is left unsplit here, and has to be accounted for should we attempt higher order perturbation calculations.

Appendix. Multipole expansion

Noting that

\begin{equation}\label{eqn:qmLecture22:700}
\begin{aligned}
\lr{1 + \epsilon}^{-1/2}
&=
1 -\inv{2} \epsilon -\inv{2}\lr{\frac{-3}{2}}\inv{2!} \epsilon^2 \\
&=
1 -\inv{2} \epsilon + \frac{3}{8} \epsilon^2,
\end{aligned}
\end{equation}

we have

\begin{equation}\label{eqn:qmLecture22:720}
\begin{aligned}
\frac{R}{\Abs{\Bepsilon + \BR}}
&=
\frac{1}{\Abs{\frac{\Bepsilon}{R} + \Rcap}} \\
&=
\lr{ 1 + 2 \frac{\Bepsilon}{R} \cdot \Rcap + \lr{\frac{\Bepsilon}{R}}^2 }^{-1/2} \\
&=
1 – \frac{\Bepsilon}{R} \cdot \Rcap -\inv{2} \lr{\frac{\Bepsilon}{R}}^2
+ \frac{3}{8}
\lr{ 2 \frac{\Bepsilon}{R} \cdot \Rcap + \lr{\frac{\Bepsilon}{R}}^2 }^2 \\
&=
1 – \frac{\Bepsilon}{R} \cdot \Rcap -\inv{2} \lr{\frac{\Bepsilon}{R}}^2
+ \frac{3}{8}
\lr{ 4 \lr{ \frac{\Bepsilon}{R} \cdot \Rcap}^2 + \lr{\frac{\Bepsilon}{R}}^4
+ 4 \frac{\Bepsilon}{R} \cdot \Rcap \lr{\frac{\Bepsilon}{R}}^2
} \\
&\approx
1 – \frac{\Bepsilon}{R} \cdot \Rcap -\inv{2} \lr{\frac{\Bepsilon}{R}}^2
+ \frac{3}{2}
\lr{ \frac{\Bepsilon}{R} \cdot \Rcap}^2 .
\end{aligned}
\end{equation}

Inserting the values from the brackets of \ref{eqn:qmLecture22:260} we have

\begin{equation}\label{eqn:qmLecture22:800}
\begin{aligned}
1
+
\frac{R}{\Abs{\Bx_1 – \Bx_2 + \BR}}
&-
\frac{R}{\Abs{\Bx_1 + \BR}}

\frac{R}{\Abs{-\Bx_2 + \BR}} \\
&=
– \frac{\lr{ \Bx_1 – \Bx_2 }}{R} \cdot \Rcap -\inv{2} \lr{\frac{\lr{ \Bx_1 – \Bx_2 }}{R}}^2
+ \frac{3}{2}
\lr{ \frac{\lr{ \Bx_1 – \Bx_2 }}{R} \cdot \Rcap}^2 \\
&\quad + \frac{\Bx_1}{R} \cdot \Rcap +\inv{2} \lr{\frac{\Bx_1}{R}}^2
– \frac{3}{2}
\lr{ \frac{\Bx_1}{R} \cdot \Rcap}^2 \\
&\quad – \frac{\Bx_2}{R} \cdot \Rcap +\inv{2} \lr{\frac{\Bx_2}{R}}^2
– \frac{3}{2}
\lr{ \frac{\Bx_2}{R} \cdot \Rcap}^2 \\
&=
\frac{\Bx_1}{R} \cdot \frac{\Bx_2 }{R}
+ \frac{3}{2}
\lr{ \frac{\lr{ \Bx_1 – \Bx_2 }}{R} \cdot \Rcap}^2 \\
&\quad
– \frac{3}{2}
\lr{ \frac{\Bx_1}{R} \cdot \Rcap}^2 \\
&\quad
– \frac{3}{2}
\lr{ \frac{\Bx_2}{R} \cdot \Rcap}^2 \\
&=
\frac{\Bx_1}{R} \cdot \frac{\Bx_2 }{R}
– 3 \frac{\Bx_1}{R} \cdot \Rcap \frac{\Bx_2}{R} \cdot \Rcap.
\end{aligned}
\end{equation}

This proves \ref{eqn:qmLecture22:280}.

References

[1] Jun John Sakurai and Jim J Napolitano. Modern quantum mechanics. Pearson Higher Ed, 2014.

Simplest perturbation two by two Hamiltonian

December 7, 2015 phy1520 No comments , , ,

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Q: two state Hamiltonian.

Given a two-state system

\begin{equation}\label{eqn:simplestTwoByTwoPerturbation:20}
H = H_0 + \lambda V
=
\begin{bmatrix}
E_1 & \lambda \Delta \\
\lambda \Delta & E_2
\end{bmatrix}
\end{equation}

  • (a) Solve the system exactly.
  • (b) Find the first order perturbed states and second order energy shifts, and compare to the exact solution.
  • (c) Solve the degenerate case for \( E_1 = E_2 \), and compare to the exact solution.

A: part (a)

The energy eigenvalues \( \epsilon \) are given by

\begin{equation}\label{eqn:simplestTwoByTwoPerturbation:40}
0
=
\lr{ E_1 – \epsilon }
\lr{ E_2 – \epsilon }
– (\lambda \Delta)^2,
\end{equation}

or

\begin{equation}\label{eqn:simplestTwoByTwoPerturbation:60}
\epsilon^2 – \epsilon\lr{ E_1 + E_2 } + E_1 E_2 = (\lambda \Delta)^2.
\end{equation}

After rearranging this is
\begin{equation}\label{eqn:simplestTwoByTwoPerturbation:80}
\epsilon = \frac{ E_1 + E_2 }{2} \pm \sqrt{ \lr{ \frac{ E_1 – E_2 }{2} }^2 + (\lambda \Delta)^2 }.
\end{equation}

Notice that for \( E_2 = E_1 \) we have

\begin{equation}\label{eqn:simplestTwoByTwoPerturbation:100}
\epsilon = E_1 \pm \lambda \Delta.
\end{equation}

Since a change of basis can always put the problem in a form so that \( E_1 > E_2 \), let’s assume that to make an approximation of the energy eigenvalues for \( \Abs{\lambda \Delta} \ll \ifrac{ (E_1 – E_2) }{2} \)

\begin{equation}\label{eqn:simplestTwoByTwoPerturbation:120}
\begin{aligned}
\epsilon
&=
\frac{ E_1 + E_2 }{2} \pm \frac{ E_1 – E_2 }{2} \sqrt{ 1 + \frac{(2 \lambda \Delta)^2}{(E_1 – E_2)^2} } \\
&\approx
\frac{ E_1 + E_2 }{2} \pm \frac{ E_1 – E_2 }{2} \lr{ 1 + 2 \frac{(\lambda
\Delta)^2}{(E_1 – E_2)^2} } \\
&=
\frac{ E_1 + E_2 }{2} \pm \frac{ E_1 – E_2 }{2}
\pm
\frac{(\lambda \Delta)^2}{E_1 – E_2} \\
&=
E_1 + \frac{(\lambda \Delta)^2}{E_1 – E_2}, E_2 + \frac{(\lambda \Delta)^2}{E_2 – E_1}.
\end{aligned}
\end{equation}

For the perturbed states, starting with the plus case, if

\begin{equation}\label{eqn:simplestTwoByTwoPerturbation:140}
\ket{+} \propto
\begin{bmatrix}
a \\
b
\end{bmatrix},
\end{equation}

we must have
\begin{equation}\label{eqn:simplestTwoByTwoPerturbation:160}
\begin{aligned}
0
&=
\biglr{ E_1 – \lr{ E_1 + \frac{(\lambda \Delta)^2}{E_1 – E_2} } } a + \lambda
\Delta b \\
&=
\biglr{ – \frac{(\lambda \Delta)^2}{E_1 – E_2} } a + \lambda \Delta b,
\end{aligned}
\end{equation}

so

\begin{equation}\label{eqn:simplestTwoByTwoPerturbation:180}
\ket{+} \rightarrow
\begin{bmatrix}
1 \\
\frac{\lambda \Delta}{E_1 – E_2}
\end{bmatrix}
= \ket{+} + \frac{\lambda \Delta}{E_1 – E_2} \ket{-}.
\end{equation}

Similarly for the minus case we must have

\begin{equation}\label{eqn:simplestTwoByTwoPerturbation:200}
\begin{aligned}
0
&=
\lambda \Delta a + \biglr{ E_2 – \lr{ E_2 + \frac{(\lambda \Delta)^2}{E_2 – E_1} } } b \\
&=
\lambda \Delta b + \biglr{ – \frac{(\lambda \Delta)^2}{E_2 – E_1} } b,
\end{aligned}
\end{equation}

for
\begin{equation}\label{eqn:simplestTwoByTwoPerturbation:220}
\ket{-} \rightarrow
\ket{-} + \frac{\lambda \Delta}{E_2 – E_1} \ket{+}.
\end{equation}

A: part (b)

For the perturbation the first energy shift for perturbation of the \( \ket{+} \) state is

\begin{equation}\label{eqn:simplestTwoByTwoPerturbation:240}
\begin{aligned}
E_{+}^{(1)}
&= \ket{+} V \ket{+} \\
&=
\lambda \Delta
\begin{bmatrix}
1 & 0
\end{bmatrix}
\begin{bmatrix}
0 & 1 \\
1 & 0
\end{bmatrix}
\begin{bmatrix}
1 \\
0
\end{bmatrix} \\
&=
\lambda \Delta
\begin{bmatrix}
1 & 0
\end{bmatrix}
\begin{bmatrix}
0 \\
1
\end{bmatrix} \\
&=
0.
\end{aligned}
\end{equation}

The first order energy shift for the perturbation of the \( \ket{-} \) state is also zero. The perturbed \( \ket{+} \) state is

\begin{equation}\label{eqn:simplestTwoByTwoPerturbation:260}
\begin{aligned}
\ket{+}^{(1)}
&= \frac{\overline{{P}}_{+}}{E_1 – H_0} V \ket{+} \\
&= \frac{\ket{-}\bra{-}}{E_1 – E_2} V \ket{+}
\end{aligned}
\end{equation}

The numerator matrix element is

\begin{equation}\label{eqn:simplestTwoByTwoPerturbation:280}
\begin{aligned}
\bra{-} V \ket{+}
&=
\begin{bmatrix}
0 & 1
\end{bmatrix}
\begin{bmatrix}
0 & \Delta \\
\Delta & 0
\end{bmatrix}
\begin{bmatrix}
1 \\
0
\end{bmatrix} \\
&=
\begin{bmatrix}
0 & 1
\end{bmatrix}
\begin{bmatrix}
0 \\
\Delta
\end{bmatrix} \\
&=
\Delta,
\end{aligned}
\end{equation}

so

\begin{equation}\label{eqn:simplestTwoByTwoPerturbation:300}
\ket{+} \rightarrow \ket{+} + \ket{-} \frac{\Delta}{E_1 – E_2}.
\end{equation}

Observe that this matches the first order series expansion of the exact value above.

For the perturbation of \( \ket{-} \) we need the matrix element

\begin{equation}\label{eqn:simplestTwoByTwoPerturbation:320}
\begin{aligned}
\bra{+} V \ket{-}
&=
\begin{bmatrix}
1 & 0
\end{bmatrix}
\begin{bmatrix}
0 & \Delta \\
\Delta & 0
\end{bmatrix}
\begin{bmatrix}
0 \\
1
\end{bmatrix} \\
&=
\begin{bmatrix}
1 & 0
\end{bmatrix}
\begin{bmatrix}
\Delta \\
0 \\
\end{bmatrix} \\
&=
\Delta,
\end{aligned}
\end{equation}

so it’s clear that the perturbed ket is

\begin{equation}\label{eqn:simplestTwoByTwoPerturbation:340}
\ket{-} \rightarrow \ket{-} + \ket{+} \frac{\Delta}{E_2 – E_1},
\end{equation}

also matching the approximation found from the exact computation. The second order energy shifts can now be calculated

\begin{equation}\label{eqn:simplestTwoByTwoPerturbation:360}
\begin{aligned}
\bra{+} V \ket{+}’
&=
\begin{bmatrix}
1 & 0
\end{bmatrix}
\begin{bmatrix}
0 & \Delta \\
\Delta & 0
\end{bmatrix}
\begin{bmatrix}
1 \\
\frac{\Delta}{E_1 – E_2}
\end{bmatrix} \\
&=
\begin{bmatrix}
1 & 0
\end{bmatrix}
\begin{bmatrix}
\frac{\Delta^2}{E_1 – E_2} \\
\Delta
\end{bmatrix} \\
&=
\frac{\Delta^2}{E_1 – E_2},
\end{aligned}
\end{equation}

and

\begin{equation}\label{eqn:simplestTwoByTwoPerturbation:380}
\begin{aligned}
\bra{-} V \ket{-}’
&=
\begin{bmatrix}
0 & 1
\end{bmatrix}
\begin{bmatrix}
0 & \Delta \\
\Delta & 0
\end{bmatrix}
\begin{bmatrix}
\frac{\Delta}{E_2 – E_1} \\
1 \\
\end{bmatrix} \\
&=
\begin{bmatrix}
0 & 1
\end{bmatrix}
\begin{bmatrix}
\Delta \\
\frac{\Delta^2}{E_2 – E_1} \\
\end{bmatrix} \\
&=
\frac{\Delta^2}{E_2 – E_1},
\end{aligned}
\end{equation}

The energy perturbations are therefore
\begin{equation}\label{eqn:simplestTwoByTwoPerturbation:400}
\begin{aligned}
E_1 &\rightarrow E_1 + \frac{(\lambda \Delta)^2}{E_1 – E_2} \\
E_2 &\rightarrow E_2 + \frac{(\lambda \Delta)^2}{E_2 – E_1}.
\end{aligned}
\end{equation}

This is what we had by approximating the exact case.

A: part (c)

For the \( E_2 = E_1 \) case, we’ll have to diagonalize the perturbation potential. That is

\begin{equation}\label{eqn:simplestTwoByTwoPerturbation:420}
\begin{aligned}
V &= U \bigwedge U^\dagger \\
\bigwedge &=
\begin{bmatrix}
\Delta & 0 \\
0 & -\Delta
\end{bmatrix} \\
U &= U^\dagger = \inv{\sqrt{2}}
\begin{bmatrix}
1 & 1 \\
1 & -1
\end{bmatrix}.
\end{aligned}
\end{equation}

A change of basis for the Hamiltonian is

\begin{equation}\label{eqn:simplestTwoByTwoPerturbation:440}
\begin{aligned}
H’
&=
U^\dagger H U \\
&=
U^\dagger H_0 U + \lambda U^\dagger V U \\
&=
E_1 U^\dagger + \lambda U^\dagger V U \\
&=
H_0 + \lambda \bigwedge.
\end{aligned}
\end{equation}

We can now calculate the perturbation energy with respect to the new basis, say \( \setlr{ \ket{1}, \ket{2} } \). Those energy shifts are

\begin{equation}\label{eqn:simplestTwoByTwoPerturbation:460}
\begin{aligned}
\Delta^{(1)} &= \bra{1} V \ket{1} = \Delta \\
\Delta^{(2)} &= \bra{2} V \ket{2} = -\Delta.
\end{aligned}
\end{equation}

The perturbed energies are therefore

\begin{equation}\label{eqn:simplestTwoByTwoPerturbation:480}
\begin{aligned}
E_1 &\rightarrow E_1 + \lambda \Delta \\
E_2 &\rightarrow E_2 – \lambda \Delta,
\end{aligned}
\end{equation}

which matches \ref{eqn:simplestTwoByTwoPerturbation:100}, the exact result.

References

PHY1520H Graduate Quantum Mechanics. Lecture 20: Perturbation theory. Taught by Prof. Arun Paramekanti

December 3, 2015 phy1520 No comments , , , , , , , , , ,

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Disclaimer

Peeter’s lecture notes from class. These may be incoherent and rough.

These are notes for the UofT course PHY1520, Graduate Quantum Mechanics, taught by Prof. Paramekanti, covering [1] ch. 5 content.

Perturbation theory

Given a \( 2 \times 2 \) Hamiltonian \( H = H_0 + V \), where

\begin{equation}\label{eqn:qmLecture20:20}
H =
\begin{bmatrix}
a & c \\
c^\conj & b
\end{bmatrix}
\end{equation}

which has eigenvalues

\begin{equation}\label{eqn:qmLecture20:40}
\lambda_\pm = \frac{a + b}{2} \pm \sqrt{ \lr{ \frac{a – b}{2}}^2 + \Abs{c}^2 }.
\end{equation}

If \( c = 0 \),

\begin{equation}\label{eqn:qmLecture20:60}
H_0 =
\begin{bmatrix}
a & 0 \\
0 & b
\end{bmatrix},
\end{equation}

so

\begin{equation}\label{eqn:qmLecture20:80}
V =
\begin{bmatrix}
0 & c \\
c^\conj & 0
\end{bmatrix}.
\end{equation}

Suppose that \( \Abs{c} \ll \Abs{a – b} \), then

\begin{equation}\label{eqn:qmLecture20:100}
\lambda_\pm \approx \frac{a + b}{2} \pm \Abs{ \frac{a – b}{2} } \lr{ 1 + 2 \frac{\Abs{c}^2}{\Abs{a – b}^2} }.
\end{equation}

If \( a > b \), then

\begin{equation}\label{eqn:qmLecture20:120}
\lambda_\pm \approx \frac{a + b}{2} \pm \frac{a – b}{2} \lr{ 1 + 2 \frac{\Abs{c}^2}{\lr{a – b}^2} }.
\end{equation}

\begin{equation}\label{eqn:qmLecture20:140}
\begin{aligned}
\lambda_{+}
&= \frac{a + b}{2} + \frac{a – b}{2} \lr{ 1 + 2 \frac{\Abs{c}^2}{\lr{a – b}^2} } \\
&= a + \lr{a – b} \frac{\Abs{c}^2}{\lr{a – b}^2} \\
&= a + \frac{\Abs{c}^2}{a – b},
\end{aligned}
\end{equation}

and
\begin{equation}\label{eqn:qmLecture20:680}
\begin{aligned}
\lambda_{-}
&= \frac{a + b}{2} – \frac{a – b}{2} \lr{ 1 + 2 \frac{\Abs{c}^2}{\lr{a – b}^2} } \\
&=
b + \lr{a – b} \frac{\Abs{c}^2}{\lr{a – b}^2} \\
&= b + \frac{\Abs{c}^2}{a – b}.
\end{aligned}
\end{equation}

This adiabatic evolution displays a “level repulsion”, quadradic in \( \Abs{c} \) as sketched in fig. 1, and is described as a non-degenerate perbutation.

fig. 1.  Adiabatic (non-degenerate) perturbation

fig. 1. Adiabatic (non-degenerate) perturbation

If \( \Abs{c} \gg \Abs{a -b} \), then

\begin{equation}\label{eqn:qmLecture20:160}
\begin{aligned}
\lambda_\pm
&= \frac{a + b}{2} \pm \Abs{c} \sqrt{ 1 + \inv{\Abs{c}^2} \lr{ \frac{a – b}{2}}^2 } \\
&\approx \frac{a + b}{2} \pm \Abs{c} \lr{ 1 + \inv{2 \Abs{c}^2} \lr{ \frac{a – b}{2}}^2 } \\
&= \frac{a + b}{2} \pm \Abs{c} \pm \frac{\lr{a – b}^2}{8 \Abs{c}}.
\end{aligned}
\end{equation}

Here we loose the adiabaticity, and have “level repulsion” that is linear in \( \Abs{c} \), as sketched in fig. 2. We no longer have the sign of \( a – b \) in the expansion. This is described as a degenerate perbutation.

fig. 2.  Degenerate perbutation

fig. 2. Degenerate perbutation

General non-degenerate perturbation

Given an unperturbed system with solutions of the form

\begin{equation}\label{eqn:qmLecture20:180}
H_0 \ket{n^{(0)}} = E_n^{(0)} \ket{n^{(0)}},
\end{equation}

we want to solve the perturbed Hamiltonian equation

\begin{equation}\label{eqn:qmLecture20:200}
\lr{ H_0 + \lambda V } \ket{ n } = \lr{ E_n^{(0)} + \Delta n } \ket{n}.
\end{equation}

Here \( \Delta n \) is an energy shift as that goes to zero as \( \lambda \rightarrow 0 \). We can write this as

\begin{equation}\label{eqn:qmLecture20:220}
\lr{ E_n^{(0)} – H_0 } \ket{ n } = \lr{ \lambda V – \Delta_n } \ket{n}.
\end{equation}

We are hoping to iterate with application of the inverse to an initial estimate of \( \ket{n} \)

\begin{equation}\label{eqn:qmLecture20:240}
\ket{n} = \lr{ E_n^{(0)} – H_0 }^{-1} \lr{ \lambda V – \Delta_n } \ket{n}.
\end{equation}

This gets us into trouble if \( \lambda \rightarrow 0 \), which can be fixed by using

\begin{equation}\label{eqn:qmLecture20:260}
\ket{n} = \lr{ E_n^{(0)} – H_0 }^{-1} \lr{ \lambda V – \Delta_n } \ket{n} + \ket{ n^{(0)} },
\end{equation}

which can be seen to be a solution to \ref{eqn:qmLecture20:220}. We want to ask if

\begin{equation}\label{eqn:qmLecture20:280}
\lr{ \lambda V – \Delta_n } \ket{n} ,
\end{equation}

contains a bit of \( \ket{ n^{(0)} } \)? To determine this act with \( \bra{n^{(0)}} \) on the left

\begin{equation}\label{eqn:qmLecture20:300}
\begin{aligned}
\bra{ n^{(0)} } \lr{ \lambda V – \Delta_n } \ket{n}
&=
\bra{ n^{(0)} } \lr{ E_n^{(0)} – H_0 } \ket{n} \\
&=
\lr{ E_n^{(0)} – E_n^{(0)} } \braket{n^{(0)}}{n} \\
&=
0.
\end{aligned}
\end{equation}

This shows that \( \ket{n} \) is entirely orthogonal to \( \ket{n^{(0)}} \).

Define a projection operator

\begin{equation}\label{eqn:qmLecture20:320}
P_n = \ket{n^{(0)}}\bra{n^{(0)}},
\end{equation}

which has the idempotent property \( P_n^2 = P_n \) that we expect of a projection operator.

Define a rejection operator
\begin{equation}\label{eqn:qmLecture20:340}
\overline{{P}}_n
= 1 –
\ket{n^{(0)}}\bra{n^{(0)}}
= \sum_{m \ne n}
\ket{m^{(0)}}\bra{m^{(0)}}.
\end{equation}

Because \( \ket{n} \) has no component in the direction \( \ket{n^{(0)}} \), the rejection operator can be inserted much like we normally do with the identity operator, yielding

\begin{equation}\label{eqn:qmLecture20:360}
\ket{n}’ = \lr{ E_n^{(0)} – H_0 }^{-1} \overline{{P}}_n \lr{ \lambda V – \Delta_n } \ket{n} + \ket{ n^{(0)} },
\end{equation}

valid for any initial \( \ket{n} \).

Power series perturbation expansion

Instead of iterating, suppose that the unknown state and unknown energy difference operator can be expanded in a \( \lambda \) power series, say

\begin{equation}\label{eqn:qmLecture20:380}
\ket{n}
=
\ket{n_0}
+ \lambda \ket{n_1}
+ \lambda^2 \ket{n_2}
+ \lambda^3 \ket{n_3} + \cdots
\end{equation}

and

\begin{equation}\label{eqn:qmLecture20:400}
\Delta_{n} = \Delta_{n_0}
+ \lambda \Delta_{n_1}
+ \lambda^2 \Delta_{n_2}
+ \lambda^3 \Delta_{n_3} + \cdots
\end{equation}

We usually interpret functions of operators in terms of power series expansions. In the case of \( \lr{ E_n^{(0)} – H_0 }^{-1} \), we have a concrete interpretation when acting on one of the unpertubed eigenstates

\begin{equation}\label{eqn:qmLecture20:420}
\inv{ E_n^{(0)} – H_0 } \ket{m^{(0)}} =
\inv{ E_n^{(0)} – E_m^0 } \ket{m^{(0)}}.
\end{equation}

This gives

\begin{equation}\label{eqn:qmLecture20:440}
\ket{n}
=
\inv{ E_n^{(0)} – H_0 }
\sum_{m \ne n}
\ket{m^{(0)}}\bra{m^{(0)}}
\lr{ \lambda V – \Delta_n } \ket{n} + \ket{ n^{(0)} },
\end{equation}

or

\begin{equation}\label{eqn:qmLecture20:460}
\boxed{
\ket{n}
=
\ket{ n^{(0)} }
+
\sum_{m \ne n}
\frac{\ket{m^{(0)}}\bra{m^{(0)}}}
{
E_n^{(0)} – E_m^{(0)}
}
\lr{ \lambda V – \Delta_n } \ket{n}.
}
\end{equation}

From \ref{eqn:qmLecture20:220}, note that

\begin{equation}\label{eqn:qmLecture20:500}
\Delta_n =
\frac{\bra{n^{(0)}} \lambda V \ket{n}}{\braket{n^0}{n}},
\end{equation}

however, we will normalize by setting \( \braket{n^0}{n} = 1 \), so

\begin{equation}\label{eqn:qmLecture20:521}
\boxed{
\Delta_n =
\bra{n^{(0)}} \lambda V \ket{n}.
}
\end{equation}

to \( O(\lambda^0) \)

If all \( \lambda^n, n > 0 \) are zero, then we have

\label{eqn:qmLecture20:780}
\begin{equation}\label{eqn:qmLecture20:740}
\ket{n_0}
=
\ket{ n^{(0)} }
+
\sum_{m \ne n}
\frac{\ket{m^{(0)}}\bra{m^{(0)}}}
{
E_n^{(0)} – E_m^{(0)}
}
\lr{ – \Delta_{n_0} } \ket{n_0}
\end{equation}
\begin{equation}\label{eqn:qmLecture20:800}
\Delta_{n_0} \braket{n^{(0)}}{n_0} = 0
\end{equation}

so

\begin{equation}\label{eqn:qmLecture20:540}
\begin{aligned}
\ket{n_0} &= \ket{n^{(0)}} \\
\Delta_{n_0} &= 0.
\end{aligned}
\end{equation}

to \( O(\lambda^1) \)

Requiring identity for all \( \lambda^1 \) terms means

\begin{equation}\label{eqn:qmLecture20:760}
\ket{n_1} \lambda
=
\sum_{m \ne n}
\frac{\ket{m^{(0)}}\bra{m^{(0)}}}
{
E_n^{(0)} – E_m^{(0)}
}
\lr{ \lambda V – \Delta_{n_1} \lambda } \ket{n_0},
\end{equation}

so

\begin{equation}\label{eqn:qmLecture20:560}
\ket{n_1}
=
\sum_{m \ne n}
\frac{
\ket{m^{(0)}} \bra{ m^{(0)}}
}
{
E_n^{(0)} – E_m^{(0)}
}
\lr{ V – \Delta_{n_1} } \ket{n_0}.
\end{equation}

With the assumption that \( \ket{n^{(0)}} \) is normalized, and with the shorthand

\begin{equation}\label{eqn:qmLecture20:600}
V_{m n} = \bra{ m^{(0)}} V \ket{n^{(0)}},
\end{equation}

that is

\begin{equation}\label{eqn:qmLecture20:580}
\begin{aligned}
\ket{n_1}
&=
\sum_{m \ne n}
\frac{
\ket{m^{(0)}}
}
{
E_n^{(0)} – E_m^{(0)}
}
V_{m n}
\\
\Delta_{n_1} &= \bra{ n^{(0)} } V \ket{ n^0} = V_{nn}.
\end{aligned}
\end{equation}

to \( O(\lambda^2) \)

The second order perturbation states are found by selecting only the \( \lambda^2 \) contributions to

\begin{equation}\label{eqn:qmLecture20:820}
\lambda^2 \ket{n_2}
=
\sum_{m \ne n}
\frac{\ket{m^{(0)}}\bra{m^{(0)}}}
{
E_n^{(0)} – E_m^{(0)}
}
\lr{ \lambda V – (\lambda \Delta_{n_1} + \lambda^2 \Delta_{n_2}) }
\lr{
\ket{n_0}
+ \lambda \ket{n_1}
}.
\end{equation}

Because \( \ket{n_0} = \ket{n^{(0)}} \), the \( \lambda^2 \Delta_{n_2} \) is killed, leaving

\begin{equation}\label{eqn:qmLecture20:840}
\begin{aligned}
\ket{n_2}
&=
\sum_{m \ne n}
\frac{\ket{m^{(0)}}\bra{m^{(0)}}}
{
E_n^{(0)} – E_m^{(0)}
}
\lr{ V – \Delta_{n_1} }
\ket{n_1} \\
&=
\sum_{m \ne n}
\frac{\ket{m^{(0)}}\bra{m^{(0)}}}
{
E_n^{(0)} – E_m^{(0)}
}
\lr{ V – \Delta_{n_1} }
\sum_{l \ne n}
\frac{
\ket{l^{(0)}}
}
{
E_n^{(0)} – E_l^{(0)}
}
V_{l n},
\end{aligned}
\end{equation}

which can be written as

\begin{equation}\label{eqn:qmLecture20:620}
\ket{n_2}
=
\sum_{l,m \ne n}
\ket{m^{(0)}}
\frac{V_{m l} V_{l n}}
{
\lr{ E_n^{(0)} – E_m^{(0)} }
\lr{ E_n^{(0)} – E_l^{(0)} }
}

\sum_{m \ne n}
\ket{m^{(0)}}
\frac{V_{n n} V_{m n}}
{
\lr{ E_n^{(0)} – E_m^{(0)} }^2
}.
\end{equation}

For the second energy perturbation we have

\begin{equation}\label{eqn:qmLecture20:860}
\lambda^2 \Delta_{n_2} =
\bra{n^{(0)}} \lambda V \lr{ \lambda \ket{n_1} },
\end{equation}

or

\begin{equation}\label{eqn:qmLecture20:880}
\begin{aligned}
\Delta_{n_2}
&=
\bra{n^{(0)}} V \ket{n_1} \\
&=
\bra{n^{(0)}} V
\sum_{m \ne n}
\frac{
\ket{m^{(0)}}
}
{
E_n^{(0)} – E_m^{(0)}
}
V_{m n}.
\end{aligned}
\end{equation}

That is

\begin{equation}\label{eqn:qmLecture20:900}
\Delta_{n_2}
=
\sum_{m \ne n} \frac{V_{n m} V_{m n} }{E_n^{(0)} – E_m^{(0)}}.
\end{equation}

to \( O(\lambda^3) \)

Similarily, it can be shown that

\begin{equation}\label{eqn:qmLecture20:640}
\Delta_{n_3} =
\sum_{l, m \ne n} \frac{V_{n m} V_{m l} V_{l n} }{
\lr{ E_n^{(0)} – E_m^{(0)} }
\lr{ E_n^{(0)} – E_l^{(0)} }
}

\sum_{ m \ne n} \frac{V_{n m} V_{n n} V_{m n} }{
\lr{ E_n^{(0)} – E_m^{(0)} }^2
}.
\end{equation}

In general, the energy perturbation is given by

\begin{equation}\label{eqn:qmLecture20:660}
\Delta_n^{(l)} = \bra{n^{(0)}} V \ket{n^{(l-1)}}.
\end{equation}

References

[1] Jun John Sakurai and Jim J Napolitano. Modern quantum mechanics. Pearson Higher Ed, 2014.