Hamiltonian

Energy estimate for an absolute value potential

December 4, 2015 phy1520 , , ,

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Here’s a simple problem, a lot like the problem set 6 variational calculation.

Q: [1] 5.21

Estimate the lowest eigenvalue \( \lambda \) of the differential equation

\begin{equation}\label{eqn:absolutePotentialVariation:20}
\frac{d^2}{dx^2}\psi + \lr{ \lambda – \Abs{x} } \psi = 0.
\end{equation}

Using \( \alpha \) variation with the trial function

\begin{equation}\label{eqn:absolutePotentialVariation:40}
\psi =
\left\{
\begin{array}{l l}
c(\alpha – \Abs{x}) & \quad \mbox{\(\Abs{x} < \alpha \) } \\ 0 & \quad \mbox{\(\Abs{x} > \alpha \) }
\end{array}
\right.
\end{equation}

A:

First rewrite the differential equation in a Hamiltonian like fashion

\begin{equation}\label{eqn:absolutePotentialVariation:60}
H \psi = -\frac{d^2}{dx^2}\psi + \Abs{x} \psi = \lambda \psi.
\end{equation}

We need the derivatives of the trial distribution. The first derivative is

\begin{equation}\label{eqn:absolutePotentialVariation:80}
\begin{aligned}
\frac{d}{dx} \psi
&=
-c \frac{d}{dx} \Abs{x} \\
&=
-c \frac{d}{dx} \lr{ x \theta(x) – x \theta(-x) } \\
&=
-c \lr{
\theta(x) – \theta(-x)
+
x \delta(x) + x \delta(-x)
} \\
&=
-c \lr{
\theta(x) – \theta(-x)
+
2 x \delta(x)
}.
\end{aligned}
\end{equation}

The second derivative is
\begin{equation}\label{eqn:absolutePotentialVariation:100}
\begin{aligned}
\frac{d^2}{dx^2} \psi
&=
-c \frac{d}{dx} \lr{
\theta(x) – \theta(-x)
+
2 x \delta(x)
} \\
&=
-c \lr{
\delta(x) + \delta(-x)
+
2 \delta(x)
+
2 x \delta'(x)
} \\
&=
-c \lr{
4 \delta(x)
+
2 x \frac{-\delta(x) }{x}
} \\
&=
-2 c \delta(x).
\end{aligned}
\end{equation}

This gives

\begin{equation}\label{eqn:absolutePotentialVariation:120}
H \psi = -2 c \delta(x) + \Abs{x} c \lr{ \alpha – \Abs{x} }.
\end{equation}

We are now set to compute some of the inner products. The normalization is the simplest

\begin{equation}\label{eqn:absolutePotentialVariation:140}
\begin{aligned}
\braket{\psi}{\psi}
&= c^2 \int_{-\alpha}^\alpha ( \alpha – \Abs{x} )^2 dx \\
&= 2 c^2 \int_{0}^\alpha ( x – \alpha )^2 dx \\
&= 2 c^2 \int_{-\alpha}^0 u^2 du \\
&= 2 c^2 \lr{ -\frac{(-\alpha)^3}{3} } \\
&= \frac{2}{3} c^2 \alpha^3.
\end{aligned}
\end{equation}

For the energy
\begin{equation}\label{eqn:absolutePotentialVariation:160}
\begin{aligned}
\braket{\psi}{H \psi}
&=
c^2 \int dx \lr{ \alpha – \Abs{x} } \lr{ -2 \delta(x) + \Abs{x} \lr{ \alpha – \Abs{x} } } \\
&=
c^2 \lr{ – 2 \alpha + \int_{-\alpha}^\alpha dx \lr{ \alpha – \Abs{x} }^2 \Abs{x} } \\
&=
c^2 \lr{ – 2 \alpha + 2 \int_{-\alpha}^0 du u^2 \lr{ u + \alpha } } \\
&=
c^2 \lr{ – 2 \alpha + 2 \evalrange{\lr{ \frac{u^4}{4} + \alpha \frac{u^3}{3} }}{-\alpha}{0} } \\
&=
c^2 \lr{ – 2 \alpha – 2 \lr{ \frac{\alpha^4}{4} – \frac{\alpha^4}{3} } } \\
&=
c^2 \lr{ – 2 \alpha + \inv{6} \alpha^4 }.
\end{aligned}
\end{equation}

The energy estimate is

\begin{equation}\label{eqn:absolutePotentialVariation:180}
\begin{aligned}
\overline{{E}}
&=
\frac{\braket{\psi}{H \psi}}{\braket{\psi}{\psi}} \\
&=
\frac{ – 2 \alpha + \inv{6} \alpha^4 }{ \frac{2}{3} \alpha^3} \\
&=
– \frac{3}{\alpha^2} + \inv{4} \alpha.
\end{aligned}
\end{equation}

This has its minimum at
\begin{equation}\label{eqn:absolutePotentialVariation:200}
0 = -\frac{6}{\alpha^3} + \inv{4},
\end{equation}

or
\begin{equation}\label{eqn:absolutePotentialVariation:220}
\alpha = 2 \times 3^{1/3}.
\end{equation}

Back subst into the energy gives

\begin{equation}\label{eqn:absolutePotentialVariation:240}
\begin{aligned}
\overline{{E}}
&=
– \frac{3}{4 \times 3^{2/3}} + \inv{2} 3^{1/3} \\
&= \frac{3^{4/3}}{4} \\
&\approx 1.08.
\end{aligned}
\end{equation}

The problem says the exact answer is 1.019, so the variation gets within 6 %.

References

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

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

December 3, 2015 phy1520 , , , , , , , , , ,

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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.

Alternate Dirac equation representation

November 27, 2015 phy1520 , ,

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Given an alternate representation of the Dirac equation

\begin{equation}\label{eqn:diracAlternate:20}
H =
\begin{bmatrix}
m c^2 + V_0 & c \hat{p} \\
c \hat{p} & – m c^2 + V_0
\end{bmatrix},
\end{equation}

calculate the constant momentum solutions, the Heisenberg velocity operator \( \hat{v} \), and find the form of the probability density current.

Plane wave solutions

The action of the Hamiltonian on

\begin{equation}\label{eqn:diracAlternate:40}
\psi =
e^{i k x – i E t/\Hbar}
\begin{bmatrix}
\psi_1 \\
\psi_2
\end{bmatrix}
\end{equation}

is
\begin{equation}\label{eqn:diracAlternate:60}
\begin{aligned}
H \psi
&=
\begin{bmatrix}
m c^2 + V_0 & c (-i \Hbar) i k \\
c (-i \Hbar) i k & – m c^2 + V_0
\end{bmatrix}
\begin{bmatrix}
\psi_1 \\
\psi_2
\end{bmatrix}
e^{i k x – i E t/\Hbar} \\
&=
\begin{bmatrix}
m c^2 + V_0 & c \Hbar k \\
c \Hbar k & – m c^2 + V_0
\end{bmatrix}
\psi.
\end{aligned}
\end{equation}

Writing

\begin{equation}\label{eqn:diracAlternate:80}
H_k
=
\begin{bmatrix}
m c^2 + V_0 & c \Hbar k \\
c \Hbar k & – m c^2 + V_0
\end{bmatrix}
\end{equation}

the characteristic equation is

\begin{equation}\label{eqn:diracAlternate:100}
0
=
(m c^2 + V_0 – \lambda)
(-m c^2 + V_0 – \lambda)
– (c \Hbar k)^2
=
\lr{ (\lambda – V_0)^2 – (m c^2)^2 } – (c \Hbar k)^2,
\end{equation}

so

\begin{equation}\label{eqn:diracAlternate:120}
\lambda = V_0 \pm \epsilon,
\end{equation}

where
\begin{equation}\label{eqn:diracAlternate:140}
\epsilon^2 = (m c^2)^2 + (c \Hbar k)^2.
\end{equation}

We’ve got

\begin{equation}\label{eqn:diracAlternate:160}
\begin{aligned}
H – ( V_0 + \epsilon )
&=
\begin{bmatrix}
m c^2 – \epsilon & c \Hbar k \\
c \Hbar k & – m c^2 – \epsilon
\end{bmatrix} \\
H – ( V_0 – \epsilon )
&=
\begin{bmatrix}
m c^2 + \epsilon & c \Hbar k \\
c \Hbar k & – m c^2 + \epsilon
\end{bmatrix},
\end{aligned}
\end{equation}

so the eigenkets are

\begin{equation}\label{eqn:diracAlternate:180}
\begin{aligned}
\ket{V_0+\epsilon}
&\propto
\begin{bmatrix}
-c \Hbar k \\
m c^2 – \epsilon
\end{bmatrix} \\
\ket{V_0-\epsilon}
&\propto
\begin{bmatrix}
-c \Hbar k \\
m c^2 + \epsilon
\end{bmatrix}.
\end{aligned}
\end{equation}

Up to an arbitrary phase for each, these are

\begin{equation}\label{eqn:diracAlternate:200}
\begin{aligned}
\ket{V_0 + \epsilon}
&=
\inv{\sqrt{ 2 \epsilon ( \epsilon – m c^2) }}
\begin{bmatrix}
c \Hbar k \\
\epsilon -m c^2
\end{bmatrix} \\
\ket{V_0 – \epsilon}
&=
\inv{\sqrt{ 2 \epsilon ( \epsilon + m c^2) }}
\begin{bmatrix}
-c \Hbar k \\
\epsilon + m c^2
\end{bmatrix} \\
\end{aligned}
\end{equation}

We can now write

\begin{equation}\label{eqn:diracAlternate:220}
H_k =
E
\begin{bmatrix}
V_0 + \epsilon & 0 \\
0 & V_0 – \epsilon
\end{bmatrix}
E^{-1},
\end{equation}

where
\begin{equation}\label{eqn:diracAlternate:240}
\begin{aligned}
E &=
\inv{\sqrt{2 \epsilon} }
\begin{bmatrix}
\frac{c \Hbar k}{ \sqrt{ \epsilon – m c^2 } } & -\frac{c \Hbar k}{ \sqrt{ \epsilon + m c^2 } } \\
\sqrt{ \epsilon – m c^2 } & \sqrt{ \epsilon + m c^2 }
\end{bmatrix}, \qquad k > 0 \\
E &=
\inv{\sqrt{2 \epsilon} }
\begin{bmatrix}
-\frac{c \Hbar k}{ \sqrt{ \epsilon – m c^2 } } & -\frac{c \Hbar k}{ \sqrt{ \epsilon + m c^2 } } \\
-\sqrt{ \epsilon – m c^2 } & \sqrt{ \epsilon + m c^2 }
\end{bmatrix}, \qquad k < 0. \end{aligned} \end{equation} Here the signs have been adjusted to ensure the transformation matrix has a unit determinant. Observe that there's redundancy in this matrix since \( \ifrac{c \Hbar \Abs{k}}{ \sqrt{ \epsilon - m c^2 } } = \sqrt{ \epsilon + m c^2 } \), and \( \ifrac{c \Hbar \Abs{k}}{ \sqrt{ \epsilon + m c^2 } } = \sqrt{ \epsilon - m c^2 } \), which allows the transformation matrix to be written in the form of a rotation matrix \begin{equation}\label{eqn:diracAlternate:260} \begin{aligned} E &= \inv{\sqrt{2 \epsilon} } \begin{bmatrix} \frac{c \Hbar k}{ \sqrt{ \epsilon - m c^2 } } & -\frac{c \Hbar k}{ \sqrt{ \epsilon + m c^2 } } \\ \frac{c \Hbar k}{ \sqrt{ \epsilon + m c^2 } } & \frac{c \Hbar k}{ \sqrt{ \epsilon - m c^2 } } \end{bmatrix}, \qquad k > 0 \\
E &=
\inv{\sqrt{2 \epsilon} }
\begin{bmatrix}
-\frac{c \Hbar k}{ \sqrt{ \epsilon – m c^2 } } & -\frac{c \Hbar k}{ \sqrt{ \epsilon + m c^2 } } \\
\frac{c \Hbar k}{ \sqrt{ \epsilon + m c^2 } } & -\frac{c \Hbar k}{ \sqrt{ \epsilon – m c^2 } }
\end{bmatrix}, \qquad k < 0 \\ \end{aligned} \end{equation} With \begin{equation}\label{eqn:diracAlternate:280} \begin{aligned} \cos\theta &= \frac{c \Hbar \Abs{k}}{ \sqrt{ 2 \epsilon( \epsilon - m c^2) } } = \frac{\sqrt{ \epsilon + m c^2} }{ \sqrt{ 2 \epsilon}}\\ \sin\theta &= \frac{c \Hbar k}{ \sqrt{ 2 \epsilon( \epsilon + m c^2) } } = \frac{\textrm{sgn}(k) \sqrt{ \epsilon - m c^2}}{ \sqrt{ 2 \epsilon } }, \end{aligned} \end{equation} the transformation matrix (and eigenkets) is \begin{equation}\label{eqn:diracAlternate:300} \boxed{ E = \begin{bmatrix} \ket{V_0 + \epsilon} & \ket{V_0 - \epsilon} \end{bmatrix} = \begin{bmatrix} \cos\theta & -\sin\theta \\ \sin\theta & \cos\theta \end{bmatrix}. } \end{equation} Observe that \ref{eqn:diracAlternate:280} can be simplified by using double angle formulas \begin{equation}\label{eqn:diracAlternate:320} \begin{aligned} \cos(2 \theta) &= \frac{\lr{ \epsilon + m c^2} }{ 2 \epsilon } - \frac{\lr{ \epsilon - m c^2}}{ 2 \epsilon } \\ &= \frac{1}{ 2 \epsilon } \lr{ \epsilon + m c^2 - \epsilon + m c^2 } \\ &= \frac{m c^2 }{ \epsilon }, \end{aligned} \end{equation} and \begin{equation}\label{eqn:diracAlternate:340} \sin(2\theta) = 2 \frac{1}{2 \epsilon} \textrm{sgn}(k ) \sqrt{ \epsilon^2 - (m c^2)^2 } = \frac{\Hbar k c}{\epsilon}. \end{equation} This allows all the \( \theta \) dependence on \( \Hbar k c \) and \( m c^2 \) to be expressed as a ratio of momenta \begin{equation}\label{eqn:diracAlternate:360} \boxed{ \tan(2\theta) = \frac{\Hbar k}{m c}. } \end{equation}

Hyperbolic solutions

For a wave function of the form

\begin{equation}\label{eqn:diracAlternate:380}
\psi =
e^{k x – i E t/\Hbar}
\begin{bmatrix}
\psi_1 \\
\psi_2
\end{bmatrix},
\end{equation}

some of the work above can be recycled if we substitute \( k \rightarrow -i k \), which yields unnormalized eigenfunctions

\begin{equation}\label{eqn:diracAlternate:400}
\begin{aligned}
\ket{V_0+\epsilon}
&\propto
\begin{bmatrix}
i c \Hbar k \\
m c^2 – \epsilon
\end{bmatrix} \\
\ket{V_0-\epsilon}
&\propto
\begin{bmatrix}
i c \Hbar k \\
m c^2 + \epsilon
\end{bmatrix},
\end{aligned}
\end{equation}

where

\begin{equation}\label{eqn:diracAlternate:420}
\epsilon^2 = (m c^2)^2 – (c \Hbar k)^2.
\end{equation}

The squared magnitude of these wavefunctions are

\begin{equation}\label{eqn:diracAlternate:440}
\begin{aligned}
(c \Hbar k)^2 + (m c^2 \mp \epsilon)^2
&=
(c \Hbar k)^2 + (m c^2)^2 + \epsilon^2 \mp 2 m c^2 \epsilon \\
&=
(c \Hbar k)^2 + (m c^2)^2 + (m c^2)^2 \mp (c \Hbar k)^2 – 2 m c^2 \epsilon \\
&= 2 (m c^2)^2 \mp 2 m c^2 \epsilon \\
&= 2 m c^2 ( m c^2 \mp \epsilon ),
\end{aligned}
\end{equation}

so, up to a constant phase for each, the normalized kets are

\begin{equation}\label{eqn:diracAlternate:460}
\begin{aligned}
\ket{V_0+\epsilon}
&=
\inv{\sqrt{ 2 m c^2 ( m c^2 – \epsilon ) }}
\begin{bmatrix}
i c \Hbar k \\
m c^2 – \epsilon
\end{bmatrix} \\
\ket{V_0-\epsilon}
&=
\inv{\sqrt{ 2 m c^2 ( m c^2 + \epsilon ) }}
\begin{bmatrix}
i c \Hbar k \\
m c^2 + \epsilon
\end{bmatrix},
\end{aligned}
\end{equation}

After the \( k \rightarrow -i k \) substitution, \( H_k \) is not Hermitian, so these kets aren’t expected to be orthonormal, which is readily verified

\begin{equation}\label{eqn:diracAlternate:480}
\begin{aligned}
\braket{V_0+\epsilon}{V_0-\epsilon}
&=
\inv{\sqrt{ 2 m c^2 ( m c^2 – \epsilon ) }}
\inv{\sqrt{ 2 m c^2 ( m c^2 + \epsilon ) }}
\begin{bmatrix}
-i c \Hbar k &
m c^2 – \epsilon
\end{bmatrix}
\begin{bmatrix}
i c \Hbar k \\
m c^2 + \epsilon
\end{bmatrix} \\
&=
\frac{ 2 ( c \Hbar k )^2 }{2 m c^2 \sqrt{(\Hbar k c)^2} } \\
&=
\textrm{sgn}(k)
\frac{
\Hbar k }{m c } .
\end{aligned}
\end{equation}

Heisenberg velocity operator

\begin{equation}\label{eqn:diracAlternate:500}
\begin{aligned}
\hat{v}
&= \inv{i \Hbar} \antisymmetric{ \hat{x} }{ H} \\
&= \inv{i \Hbar} \antisymmetric{ \hat{x} }{ m c^2 \sigma_z + V_0 + c \hat{p} \sigma_x } \\
&= \frac{c \sigma_x}{i \Hbar} \antisymmetric{ \hat{x} }{ \hat{p} } \\
&= c \sigma_x.
\end{aligned}
\end{equation}

Probability current

Acting against a completely general wavefunction the Hamiltonian action \( H \psi \) is

\begin{equation}\label{eqn:diracAlternate:520}
\begin{aligned}
i \Hbar \PD{t}{\psi}
&= m c^2 \sigma_z \psi + V_0 \psi + c \hat{p} \sigma_x \psi \\
&= m c^2 \sigma_z \psi + V_0 \psi -i \Hbar c \sigma_x \PD{x}{\psi}.
\end{aligned}
\end{equation}

Conversely, the conjugate \( (H \psi)^\dagger \) is

\begin{equation}\label{eqn:diracAlternate:540}
-i \Hbar \PD{t}{\psi^\dagger}
= m c^2 \psi^\dagger \sigma_z + V_0 \psi^\dagger +i \Hbar c \PD{x}{\psi^\dagger} \sigma_x.
\end{equation}

These give

\begin{equation}\label{eqn:diracAlternate:560}
\begin{aligned}
i \Hbar \psi^\dagger \PD{t}{\psi}
&=
m c^2 \psi^\dagger \sigma_z \psi + V_0 \psi^\dagger \psi -i \Hbar c \psi^\dagger \sigma_x \PD{x}{\psi} \\
-i \Hbar \PD{t}{\psi^\dagger} \psi
&= m c^2 \psi^\dagger \sigma_z \psi + V_0 \psi^\dagger \psi +i \Hbar c \PD{x}{\psi^\dagger} \sigma_x \psi.
\end{aligned}
\end{equation}

Taking differences
\begin{equation}\label{eqn:diracAlternate:580}
\psi^\dagger \PD{t}{\psi} + \PD{t}{\psi^\dagger} \psi
=
– c \psi^\dagger \sigma_x \PD{x}{\psi} – c \PD{x}{\psi^\dagger} \sigma_x \psi,
\end{equation}

or

\begin{equation}\label{eqn:diracAlternate:600}
0
=
\PD{t}{}
\lr{
\psi^\dagger \psi
}
+
\PD{x}{}
\lr{
c \psi^\dagger \sigma_x \psi
}.
\end{equation}

The probability current still has the usual form \( \rho = \psi^\dagger \psi = \psi_1^\conj \psi_1 + \psi_2^\conj \psi_2 \), but the probability current with this representation of the Dirac Hamiltonian is

\begin{equation}\label{eqn:diracAlternate:620}
\begin{aligned}
j
&= c \psi^\dagger \sigma_x \psi \\
&= c
\begin{bmatrix}
\psi_1^\conj &
\psi_2^\conj
\end{bmatrix}
\begin{bmatrix}
\psi_2 \\
\psi_1
\end{bmatrix} \\
&= c \lr{ \psi_1^\conj \psi_2 + \psi_2^\conj \psi_1 }.
\end{aligned}
\end{equation}

PHY1520H Graduate Quantum Mechanics. Lecture 18: Approximation methods. Taught by Prof. Arun Paramekanti

November 26, 2015 phy1520 , ,

[Click here for a PDF of this post with nicer formatting]

Disclaimer

Peeter’s lecture notes from class. These may be incoherent and rough, especially since I didn’t attend this class myself, and am doing a walkthrough of notes provided by Nishant.

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

Approximation methods

Suppose we have a perturbed Hamiltonian

\begin{equation}\label{eqn:qmLecture18:20}
H = H_0 + \lambda V,
\end{equation}

where \( \lambda = 0 \) represents a solvable (perhaps known) system, and \( \lambda = 1 \) is the case of interest. There are two approaches of interest

  1. Direct solution of \( H \) with \( \lambda = 1 \).
  2. Take \( \lambda \) small, and do a series expansion. This is perturbation theory.

Variational methods

Given

\begin{equation}\label{eqn:qmLecture18:40}
H \ket{\phi_n} = E_n \ket{\phi_n},
\end{equation}

where we don’t know \( \ket{\phi_n} \), we can compute the expectation with respect to an arbitrary state \( \ket{\psi} \)

\begin{equation}\label{eqn:qmLecture18:60}
\bra{\psi} H \ket{\psi}
=
\bra{\psi} H \lr{ \sum_n \ket{\phi_n} \bra{\phi_n} } \ket{\psi}
=
\sum_n E_n \braket{\psi}{\phi_n} \braket{\phi_n}{\psi}
=
\sum_n E_n \Abs{\braket{\psi}{\phi_n}}^2.
\end{equation}

Define

\begin{equation}\label{eqn:qmLecture18:80}
\overline{{E}}
= \frac{\bra{\psi} H \ket{\psi}}{\braket{\psi}{\psi}}.
\end{equation}

Assuming that it is possible to express the state in the Hamiltonian energy basis

\begin{equation}\label{eqn:qmLecture18:100}
\ket{\psi}
=
\sum_n a_n \ket{\phi_n},
\end{equation}

this average energy is
\begin{equation}\label{eqn:qmLecture18:120}
\overline{{E}}
= \frac{ \sum_{m,n}\bra{\phi_m} a_m^\conj H a_n \ket{\phi_n}}{ \sum_n \Abs{a_n}^2 }
= \frac{ \sum_{n} \Abs{a_n}^2 E_n }{ \sum_n \Abs{a_n}^2 }.
= \sum_{n}
\frac{\Abs{a_n}^2 }{ \sum_n \Abs{a_n}^2 }
E_n
= \sum_n \frac{P_n}{\sum_m P_m} E_n,
\end{equation}

where \( P_m = \Abs{a_m}^2 \), which has the structure of a probability coefficient once divided by \( \sum_m P_m \), as sketched in fig. 1.

fig. 1. A decreasing probability distribution

fig. 1. A decreasing probability distribution

This average energy is a probability weighted average of the individual energy basis states. One of those energies is the ground state energy \( E_1 \), so we necessarily have

\begin{equation}\label{eqn:qmLecture18:140}
\boxed{
\overline{{E}} \ge E_1.
}
\end{equation}

Example: particle in a \( [0,L] \) box.

For the infinite potential box sketched in fig. 2.

fig. 2. Infinite potential [0,L] box.

fig. 2. Infinite potential [0,L] box.

The exact solutions for such a system are found to be

\begin{equation}\label{eqn:qmLecture18:220}
\psi(x) = \sqrt{\frac{2}{L}} \sin\lr{ \frac{n \pi}{L} x },
\end{equation}

where the energies are

\begin{equation}\label{eqn:qmLecture18:240}
E = \frac{\Hbar^2}{2m} \frac{n^2 \pi^2}{L^2}.
\end{equation}

The function \( \psi’ = x (L-x) \) also satisfies the boundary value constraints? How close in energy is that function to the ground state?

\begin{equation}\label{eqn:qmLecture18:260}
\overline{{E}}
=
-\frac{\Hbar^2}{2m} \frac{\int_0^L dx x (L-x) \frac{d^2}{dx^2} \lr{ x (L-x) }}{
\int_0^L dx x^2 (L-x)^2
}
=
\frac{\Hbar^2}{2m} \frac{\frac{2 L^3}{6}}{
\frac{L^5}{30}
}
=
\frac{\Hbar^2}{2m} \frac{10}{L^2}.
\end{equation}

This average energy is quite close to the ground state energy

\begin{equation}\label{eqn:qmLecture18:280}
\frac{\overline{{E}} }{E_1} = \frac{10}{\pi^2} = 1.014.
\end{equation}

Example II: particle in a \( [-L/2,L/2] \) box.

fig. 3. Infinite potential [-L/2,L/2] box.

fig. 3. Infinite potential [-L/2,L/2] box.

Shifting the boundaries, as sketched in fig. 3 doesn’t change the energy levels. For this potential let’s try a shifted trial function

\begin{equation}\label{eqn:qmLecture18:300}
\psi(x) = \lr{ x – \frac{L}{2} } \lr{ x + \frac{L}{2} } = x^2 – \frac{L^2}{4},
\end{equation}

without worrying about the form of the exact solution. This produces the same result as above

\begin{equation}\label{eqn:qmLecture18:270}
\overline{{E}}
=
-\frac{\Hbar^2}{2m} \frac{\int_0^L dx \lr{ x^2 – \frac{L^2}{4} } \frac{d^2}{dx^2} \lr{ x^2 – \frac{L^2}{4} }}{
\int_0^L dx \lr{x^2 – \frac{L^2}{4} }^2
}
=
-\frac{\Hbar^2}{2m} \frac{- 2 L^3/6}{
\frac{L^5}{30}
}
=
\frac{\Hbar^2}{2m} \frac{10}{L^2}.
\end{equation}

Summary (Nishant)

The above example is that of a particle in a box. The actual wave function is a sin as shown. But we can
come up with a guess wave function that meets the boundary conditions and ask how accurate it is
compared to the actual one.

Basically we are assuming a wave function form and then seeing how it differs from the exact form.
We cannot do this if we have nothing to compare it against. But, we note that the variance of the
number operator in the systems eigenstate is zero. So we can still calculate the variance and try to
minimize it. This is one way of coming up with an approximate wave function. This does not necessarily
give the ground state wave function though. For this we need to minimize the energy itself.

References

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

Two spin time evolution

November 14, 2015 phy1520 , , , ,

[Click here for a PDF of this post with nicer formatting]

Motivation

Our midterm posed a (low mark “quick question”) that I didn’t complete (or at least not properly). This shouldn’t have been a difficult question, but I spend way too much time on it, costing me time that I needed for other questions.

It turns out that there isn’t anything fancy required for this question, just perseverance and careful work.

Guts

The question asked for the time evolution of a two particle state

\begin{equation}\label{eqn:twoSpinHamiltonian:20}
\psi = \inv{\sqrt{2}} \lr{ \ket{\uparrow \downarrow} – \ket{\downarrow \uparrow} }
\end{equation}

under the action of the Hamiltonian

\begin{equation}\label{eqn:twoSpinHamiltonian:40}
H = – B S_{z,1} + 2 B S_{x,2} = \frac{\Hbar B}{2}\lr{ -\sigma_{z,1} + 2 \sigma_{x,2} } .
\end{equation}

We have to know the action of the Hamiltonian on all the states

\begin{equation}\label{eqn:twoSpinHamiltonian:60}
\begin{aligned}
H \ket{\uparrow \uparrow} &= \frac{B \Hbar}{2} \lr{ -\ket{\uparrow \uparrow} + 2 \ket{\uparrow \downarrow} } \\
H \ket{\uparrow \downarrow} &= \frac{B \Hbar}{2} \lr{ -\ket{\uparrow \downarrow} + 2 \ket{\uparrow \uparrow} } \\
H \ket{\downarrow \uparrow} &= \frac{B \Hbar}{2} \lr{ \ket{\downarrow \uparrow} + 2 \ket{\downarrow \downarrow} } \\
H \ket{\downarrow \downarrow} &= \frac{B \Hbar}{2} \lr{ \ket{\downarrow \downarrow} + 2 \ket{\downarrow \uparrow} } \\
\end{aligned}
\end{equation}

With respect to the basis \( \setlr{ \ket{\uparrow \uparrow}, \ket{\uparrow \downarrow}, \ket{\downarrow \uparrow}, \ket{\downarrow \downarrow} } \), the matrix of the Hamiltonian is

\begin{equation}\label{eqn:twoSpinHamiltonian:80}
H =
\frac{ \Hbar B }{2}
\begin{bmatrix}
-1 & 2 & 0 & 0 \\
2 & -1 & 0 & 0 \\
0 & 0 & 1 & 2 \\
0 & 0 & 2 & 1 \\
\end{bmatrix}
\end{equation}

Utilizing the block diagonal form (and ignoring the \( \Hbar B/2 \) factor for now), the characteristic equation is

\begin{equation}\label{eqn:twoSpinHamiltonian:100}
0
=
\begin{vmatrix}
-1 -\lambda & 2 \\
2 & -1 – \lambda
\end{vmatrix}
\begin{vmatrix}
1 -\lambda & 2 \\
2 & 1 – \lambda
\end{vmatrix}
=
\lr{(1 + \lambda)^2 – 4}
\lr{(1 – \lambda)^2 – 4}.
\end{equation}

This has solutions

\begin{equation}\label{eqn:twoSpinHamiltonian:120}
1 \pm \lambda = \pm 2,
\end{equation}

or, with the \( \Hbar B/2 \) factors put back in

\begin{equation}\label{eqn:twoSpinHamiltonian:140}
\lambda = \pm \Hbar B/2 , \pm 3 \Hbar B/2.
\end{equation}

I was thinking that we needed to compute the time evolution operator

\begin{equation}\label{eqn:twoSpinHamiltonian:160}
U = e^{-i H t/\Hbar},
\end{equation}

but we actually only need the eigenvectors, and the inverse relations. We can find the eigenvectors by inspection in each case from

\begin{equation}\label{eqn:twoSpinHamiltonian:180}
\begin{aligned}
H – (1) \frac{ \Hbar B }{2}
&=
\frac{ \Hbar B }{2}
\begin{bmatrix}
-2 & 2 & 0 & 0 \\
2 & -2 & 0 & 0 \\
0 & 0 & 0 & 2 \\
0 & 0 & 2 & 0 \\
\end{bmatrix} \\
H – (-1) \frac{ \Hbar B }{2}
&=
\frac{ \Hbar B }{2}
\begin{bmatrix}
0 & 2 & 0 & 0 \\
2 & 0 & 0 & 0 \\
0 & 0 & 2 & 2 \\
0 & 0 & 2 & 2 \\
\end{bmatrix} \\
H – (3) \frac{ \Hbar B }{2}
&=
\frac{ \Hbar B }{2}
\begin{bmatrix}
-4 & 2 & 0 & 0 \\
2 & -4 & 0 & 0 \\
0 & 0 &-2 & 2 \\
0 & 0 & 2 &-2 \\
\end{bmatrix} \\
H – (-3) \frac{ \Hbar B }{2}
&=
\frac{ \Hbar B }{2}
\begin{bmatrix}
2 & 2 & 0 & 0 \\
2 & 2 & 0 & 0 \\
0 & 0 & 4 & 2 \\
0 & 0 & 2 & 1 \\
\end{bmatrix}.
\end{aligned}
\end{equation}

The eigenkets are

\begin{equation}\label{eqn:twoSpinHamiltonian:280}
\begin{aligned}
\ket{1} &=
\inv{\sqrt{2}}
\begin{bmatrix}
1 \\
1 \\
0 \\
0 \\
\end{bmatrix} \\
\ket{-1} &=
\inv{\sqrt{2}}
\begin{bmatrix}
0 \\
0 \\
1 \\
-1 \\
\end{bmatrix} \\
\ket{3} &=
\inv{\sqrt{2}}
\begin{bmatrix}
0 \\
0 \\
1 \\
1 \\
\end{bmatrix} \\
\ket{-3} &=
\inv{\sqrt{2}}
\begin{bmatrix}
1 \\
-1 \\
0 \\
0 \\
\end{bmatrix},
\end{aligned}
\end{equation}

or

\begin{equation}\label{eqn:twoSpinHamiltonian:300}
\begin{aligned}
\sqrt{2} \ket{1} &= \ket{\uparrow \uparrow} + \ket{\uparrow \downarrow} \\
\sqrt{2} \ket{-1} &= \ket{\downarrow \uparrow} – \ket{\downarrow \downarrow} \\
\sqrt{2} \ket{3} &= \ket{\downarrow \uparrow} + \ket{\downarrow \downarrow} \\
\sqrt{2} \ket{-3} &= \ket{\uparrow \uparrow} – \ket{\uparrow \downarrow}.
\end{aligned}
\end{equation}

We can invert these

\begin{equation}\label{eqn:twoSpinHamiltonian:220}
\begin{aligned}
\ket{\uparrow \uparrow} &= \inv{\sqrt{2}} \lr{ \ket{1} + \ket{-3} } \\
\ket{\uparrow \downarrow} &= \inv{\sqrt{2}} \lr{ \ket{1} – \ket{-3} } \\
\ket{\downarrow \uparrow} &= \inv{\sqrt{2}} \lr{ \ket{3} + \ket{-1} } \\
\ket{\downarrow \downarrow} &= \inv{\sqrt{2}} \lr{ \ket{3} – \ket{-1} } \\
\end{aligned}
\end{equation}

The original state of interest can now be expressed in terms of the eigenkets

\begin{equation}\label{eqn:twoSpinHamiltonian:240}
\psi
=
\inv{2} \lr{
\ket{1} – \ket{-3} –
\ket{3} – \ket{-1}
}
\end{equation}

The time evolution of this ket is

\begin{equation}\label{eqn:twoSpinHamiltonian:260}
\begin{aligned}
\psi(t)
&=
\inv{2}
\lr{
e^{-i B t/2} \ket{1}
– e^{3 i B t/2} \ket{-3}
– e^{-3 i B t/2} \ket{3}
– e^{i B t/2} \ket{-1}
} \\
&=
\inv{2 \sqrt{2}}
\Biglr{
e^{-i B t/2} \lr{ \ket{\uparrow \uparrow} + \ket{\uparrow \downarrow} }
– e^{3 i B t/2} \lr{ \ket{\uparrow \uparrow} – \ket{\uparrow \downarrow} }
– e^{-3 i B t/2} \lr{ \ket{\downarrow \uparrow} + \ket{\downarrow \downarrow} }
– e^{i B t/2} \lr{ \ket{\downarrow \uparrow} – \ket{\downarrow \downarrow} }
} \\
&=
\inv{2 \sqrt{2}}
\Biglr{
\lr{ e^{-i B t/2} – e^{3 i B t/2} } \ket{\uparrow \uparrow}
+ \lr{ e^{-i B t/2} + e^{3 i B t/2} } \ket{\uparrow \downarrow}
– \lr{ e^{-3 i B t/2} + e^{i B t/2} } \ket{\downarrow \uparrow}
+ \lr{ e^{i B t/2} – e^{-3 i B t/2} } \ket{\downarrow \downarrow}
} \\
&=
\inv{2 \sqrt{2}}
\Biglr{
e^{i B t/2} \lr{ e^{-2 i B t/2} – e^{2 i B t/2} } \ket{\uparrow \uparrow}
+ e^{i B t/2} \lr{ e^{-2 i B t/2} + e^{2 i B t/2} } \ket{\uparrow \downarrow}
– e^{- i B t/2} \lr{ e^{-2 i B t/2} + e^{2 i B t/2} } \ket{\downarrow \uparrow}
+ e^{- i B t/2} \lr{ e^{2 i B t/2} – e^{-2 i B t/2} } \ket{\downarrow \downarrow}
} \\
&=
\inv{\sqrt{2}}
\lr{
i \sin( B t )
\lr{
e^{- i B t/2} \ket{\downarrow \downarrow} – e^{i B t/2} \ket{\uparrow \uparrow}
}
+ \cos( B t ) \lr{
e^{i B t/2} \ket{\uparrow \downarrow}
– e^{- i B t/2} \ket{\downarrow \uparrow}
}
}
\end{aligned}
\end{equation}

Note that this returns to the original state when \( t = \frac{2 \pi n}{B}, n \in \mathbb{Z} \). I think I’ve got it right this time (although I got a slightly different answer on paper before typing it up.)

This doesn’t exactly seem like a quick answer question, at least to me. Is there some easier way to do it?