Tony Zhang
Spring 2017
These are my lecture notes from 8.06, Quantum Mechanics III, at the
Massachusetts Institute of Technology, taught this semester (Spring 2017) by
Professor Barton Zwiebach1 . I attended recitation sections by Professor Maxim
Metlitski2 .
I wrote these lecture notes in LATEX in real time during lectures, so there
may be errors and typos. I have shamelessly pillaged Evan Chen’s formatting
commands. Should you encounter an error in the notes, wish to suggest im-
provements, or alert me to a failure on my part to keep the web notes updated,
please contact me at txz@mit.edu.
This document was last modified 2017-05-29. The permalink to these notes
is http://web.mit.edu/txz/www/links.html.
1 zwiebach@mit.edu
2 mmetlits@mit.edu
i
Tony Zhang Contents
Contents
1 February 7, 2017 2
1.1 Administrivia . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
1.2 Time-independent Perturbation Theory . . . . . . . . . . . . . . 2
1.3 Validity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
ii
Tony Zhang Contents
11 March 2, 2017 30
11.1 WKB; the semiclassical approximation . . . . . . . . . . . . . . . 30
11.2 Local momentum, de Broglie wavelength . . . . . . . . . . . . . . 31
11.3 Solving the equation . . . . . . . . . . . . . . . . . . . . . . . . . 31
11.4 Validity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 33
11.5 The connection formula . . . . . . . . . . . . . . . . . . . . . . . 33
13 March 7, 2017 36
13.1 Establishing the connection formulae . . . . . . . . . . . . . . . . 36
13.2 Arrows and asymmetric validity . . . . . . . . . . . . . . . . . . . 39
13.3 Tunneling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 39
15 March 9, 2017 42
15.1 Time-dependent perturbation theory . . . . . . . . . . . . . . . . 42
15.2 The interaction picture . . . . . . . . . . . . . . . . . . . . . . . . 42
15.3 Exact evolution in the interaction picture . . . . . . . . . . . . . 43
15.3.1 Example: two-state system . . . . . . . . . . . . . . . . . 43
15.4 Perturbative solution . . . . . . . . . . . . . . . . . . . . . . . . . 45
iii
Tony Zhang Contents
21 Apri 4, 2017 61
21.1 Einstein’s argument for spontaneous emission . . . . . . . . . . . 61
21.2 Atom-light interaction . . . . . . . . . . . . . . . . . . . . . . . . 62
23 April 6, 2017 68
23.1 Classical adiabatic change . . . . . . . . . . . . . . . . . . . . . . 68
23.2 Quantum mechanical motivation . . . . . . . . . . . . . . . . . . 69
23.3 Quantum adiabatic evolution . . . . . . . . . . . . . . . . . . . . 70
iv
Tony Zhang Contents
VI Scattering 89
33 May 2, 2017 99
33.1 More about phase shifts . . . . . . . . . . . . . . . . . . . . . . . 99
33.2 Example: hard sphere scattering . . . . . . . . . . . . . . . . . . 101
33.3 General computation of the phase shift . . . . . . . . . . . . . . . 103
33.4 Intuition for phase shifts . . . . . . . . . . . . . . . . . . . . . . . 103
33.4.1 Impact parameters . . . . . . . . . . . . . . . . . . . . . . 103
33.4.2 Partial wave unitarity . . . . . . . . . . . . . . . . . . . . 104
vi
Tony Zhang Contents
vii
Tony Zhang
Part I
Time-independent perturbation
theory
1
Tony Zhang 1 February 7, 2017
1 February 7, 2017
1.1 Administrivia
• There’s stuff on Stellar
• There will be an in-class midterm on Thursday, March 23, 2017.
• Weekly psets, due Tuesdays at 5pm.
• A term paper exists. See Stellar for more. Don’t worry about it until the
class gets busy (April).
• The structure of these lectures will follow that of Aram Harrow’s lecture
notes.
• This course is different from 8.04 or 8.05... “we do things that are more
practical here”. A lot of what we do in this course has to do with
approximation.
• hyperfine splitting
• spin-orbit coupling
• van der Waals forces
Today we’ll consider the nondegenerate case. We’ll see that it’s the simpler
case.
Let’s say we have a Hamiltonian H that we’d like to study. It turns out that
H = H 0 + δH, where we understand the original Hamiltonian H 0 really well,
and where δH is “small”.
What does it mean to be “small”? Does it mean it has small matrix elements?
Not quite.
Instead, let’s write
H(λ) = H 0 + λ δH (1.1)
where λ is a small, dimensionless number.
We assume that everything about H 0 is known. That is, we know its
spectrum
H 0 |n(0) i = En(0) |n(0) i (1.2)
for n ∈ Z. (In principle, we could have uncountable spectra too.)
(0) (0)
We impose non-degeneracy: that is, En 6= Em for n 6= m. Non-degeneracy
lets us characterize (label, “track”) our eigenstates by their eigenvalues.
We want to find the spectrum of H(λ):
2
Tony Zhang 1 February 7, 2017
(k)
In the spirit of power series, the |n(k) i and En , the unknown “coefficients”
on λ, are λ independent.
Formally,
1 ∂ k |niλ
(k)
|n i= (1.6)
k! ∂λk λ=0
(k)
and similarly for En .
Write the eigenvalue equation with these new eigenvalues and eigenvectors
as a power series in λ:
0 = (H 0 + λ δH − En (λ)) |niλ
= ((H 0 − En(0) ) − λ(En(1) − δH) − λ2 En(2) − . . . )
(|n(0) i + λ |n(1) i + λ2 |n(2) i + . . . )
Joke. “The difficulty with perturbation theory is the labels.”
The polynomial on the right hand side must vanish identically, so its coeffi-
cients all vanish:
λ0 (H 0 − En(0) ) |n(0) i = 0 (1.7)
1 0
λ (H − En(0) ) |n(1) i = (En(1) − δH) |n (0)
i (1.8)
λ2 (H 0 − En(0) ) |n(2) i = (En(1) − δH) |n(1) i + En(2) |n(0) i (1.9)
.. ..
. .
λk (H 0 − En(0) ) |n(k) i = (En(1) − δH) |n(k−1) i + En(2) |n(k−2) i + · · · + En(k) |n(0) i
(1.10)
These equations can be solved recursively.
Does |n(1) i have to be orthogonal to |n(0) i? Note that Equation 1.9, which
defines it, holds if we add arbitrary |n(0) i components on |n(1) i, by Equation 1.7.
Indeed, we can and will, without loss of generality, assume that hn(0) |n(k) i = 0
for k 6= 0.
Let’s not worry about finding the eigenvector corrections first. We’ll look for
(k)
the En .
Adjoining a hn(0) | to Equation 1.8 gives us
Some people say this is the most important practical result in quantum mechanics.
Doing the same to Equation 1.9 gives
En(2) = hn(0) |δH|n(1) i .
3
Tony Zhang 1 February 7, 2017
In general, we get
En(k) = hn(0) |δH|n(k−1) i (1.12)
OK, great, but these all require the eigenvector corrections |n(k) i. So let’s
compute those.
We resolve the identity over the spectrum of H 0 :
X
1= |k (0) i hk (0) | .
k6=n
1.3 Validity
How valid is our perturbative solution? Suppose we have H (0) = diag(E1 , E2 )
with
(0) E1 λV
H + λV̂ =
λV ∗ E2
The Taylor expansion of the square root gives some series with finite radius of
convergence (it’s 1, actually). So a perturbative expansion is only valid when
E1 − E2
λ|V |<
.
2
We see a hint of the difficulties to come when the original spectrum becomes
degenerate.
4
Tony Zhang 2 Feburary 8, 2017 (recitation)
p2A e2 p2 e2
H (0) = − + B − (2.2)
2me 4πε0 |~rA | 2me 4πε0 |~rB |
where pi are the electron momenta and ~ri are the electron displacements from
their respective nuclei. The energies are just
1 1
En,n0 = −13.6 eV +
n2 (n0 )2
(2) e2 a60
δE(1,0,0),(1,0,0) ∼ −
4πε0 a0 R6
5
Tony Zhang 3 February 14, 2017
1. The first order corected ground state energy overstates the true ground
state energy. By the Variational principle:
(0)
E0 + λ δH00 = h0(0) |(H (0) + λ δH)|0(0) i
= h0(0) |H(λ)|0(0) i
≥ E0 (λ)
6
Tony Zhang 3 February 14, 2017
Remark 3.1. To compute expressions like h0|(â + â† )4 |0i, “peel off” one term
from the operator power at a time; don’t expand the whole thing. Write it like
(â + â† )(â + â† )3 .
(2)
X |δH0k |2
E0 =− (0) (0)
.
k>0 Ek − E0
Now we want the values δH0k = 14 h̄ω h0|(a + a† )4 |ki. We make some notes:
Therefore, we only need compute δH02 and δH04 . These turn out to be:
√
3 24
δH02 = √ h̄ω δH04 = h̄ω
2 4
whence
(2) 21
E0 =− h̄ω.
8
Then our second-order result is
(0) (1) 2 (2) 1 3 21 2 3
E0 + λE0 +λ E0 = h̄ω 1 + λ − λ + O(λ )
2 2 4
People have computed this series to super-high order. It turns out that this
series fails to converge for any λ 6= 0. It’s an asymptotic expansion. While
the series doesn’t converge, it does give a good approximation if you terminate
summation early. In practice, you add to your partial sum until terms start
growing.
Joke. *I get Muses-serenaded* “I guess 8.06 students are very popular; maybe
we’ll get a third!” — Zwiebach, paraphrased
Naively, we might take the standard basis as our eigenbasis, and compute
corrections 1 + λδHii = 1. But the actual eigenvalues are 1 ± λ, with eigenvectors
√1 (1, ±1)T .
2
For arbitrarily small λ > 0, the eigenvectors change discontinuously. But
was there actually discontinuous behavior? Not really. Our original eigenvectors
actually lived in a two-dimensional subspace of eigenvectors.
7
Tony Zhang 3 February 14, 2017
Now let’s develop the general theory. So suppose now that H (0) has spectrum
(0)
in which energy En has degeneracy N . Call this eigenspace Vn , and let the
other eigenspaces’ span be V̂ , whence our total state space is H = Vn ⊕ V̂ .
Restrict attention to Vn , and take some orthonormal basis |n(0) , ki for
k = 1, . . . , N . Let |p(0) i be a basis for V̂ .
Again, assume states and energies vary continuously as
As before, assume without loss of generality that the corrections |n(j) ; ki are
orthogonal to |n(0) ; ki. They still may have components in the orthogonal
space V̂ , however.
Now using the eigenvalue equation, we have
as before.
We now assume that δH completely breaks the degeneracy to first order in
λ. Let’s see what happens when we bra Equation 3.5 with hn(0) ; l|:
(1)
0 = hn(0) , l|(En,k − δH)|n(0) , ki
(1)
hn(0) ; l|δH|n(0) , ki = En,k δlk
(1)
δHnl,nk = En,k δlk
8
Tony Zhang 4 February 16, 2017
1. Equation 3.7 is always true, even if the perturbation δH does not break
the degeneracy to first order.
2. For the results of degenerate perturbation theory to hold, δH must have
diagonal V block.
3. δH is diagonal in V if we can find some Hermitian K with [δH, K] = 0
(over our entire state space H) such that the basis vectors we chose in V
are eigenstates of K with distinct eigenvalues.
where we add the |ψn,k i (like +C in integration). It turns out that we get
inconsistencies if we do not include this term.
9
Tony Zhang 4 February 16, 2017
We don’t want to find |n(2) ; ki at this point. But let’s bra Equation 4.3 with
(0)
hn ; l| and see what we get:
(1) (2)
0 = hn(0) ; l|(En,k − δH)|n(1) ; ki + hn(0) ; l|En,k |n(0) ; ki
(1)
X δHp,nk |p(0) i
= hn(0) ; l| (En,k − δH) (0) (0)
p En − Ep
(1)
+ hn(0) ; l|(En,k − δH)|ψn,k i
(2)
+ En,k δkl
X δHp,nk δHnl,p (1) (1) (2)
0=− (0) (0)
+ (En,k − En,l ) hn(0) ; l|ψn,k i + Enk δkl (4.5)
p E n − E p
(2)
X δHnk,p δHp,nk
Enk = (0) (0)
(4.6)
p En − Ep
which gives the correct expression for the second-order energy shift.
Finally, to figure out the wavefunction correction, take k 6= l in Equation 4.5.
Then
X δHp,nk δHnl,p (1) (1)
− (0) (0)
+ (En,k − En,l ) hn(0) ; l|ψn,k i = 0
p E n − E p
which yields
1 X δHp,nk δHnl,p
hn(0) ; l|ψn,k i = (1) (1) (0) (0)
En,k − En,l p En − Ep
X |n(0) ; li X δHp,nk δHnl,p
|ψn,k i = (1) (1) (0) (0)
(4.7)
l6=k En,k − En,l p En − Ep
Wait: this equation has two factors of δH. Is that ok? Shouldn’t this be
a first-order correction? It is a first-order correction: dividing by the energy
difference “removes an order”.
Note that only here did we invoke the fact that δH breaks all degeneracy to
first order; otherwise dividing by the energy differences is invalid.
Now we don’t assume that δH breaks all degeneracy at first order: it might
still break some, but not all.
Suppose we’re again in eigenspace Vn of H (0) with dimension N . Now choose
a basis for Vn in which δH is diagonal and for which the first N 0 terms along
the diagonal of δH are all equal to Ê (1) .
10
Tony Zhang 4 February 16, 2017
(0)
with ak unknown. We now assume that this state and its eigenvalue evolve
power-series like as we vary λ (the standard perturbation theory assumption):
Now assume X
|ψ (1) i = |r(0) i a(1)
r + stuff in V2
r
(1)
where the ar are unknown. Now bra-ing Equation 4.2 with hp(0) |, find that
0
N
1 X (0)
a(1)
p = (0) (0)
δHp,nk ak . (4.8)
En − Ep k=1
(2)
which we recognize as an eigenvalue equation. If the En are all distinct, then
(0)
we’re good! We’d have a bunch of {ak }1≤k≤N 0 that would give eigenvectors
living in V1 . This would tell us what basis we should use
Reviewing the logic:
11
Tony Zhang 5 February 21, 2017 (recitation)
p2x 1 p2y 1
H0 = + mω 2 x2 + + mω 2 y 2
2m 2 2m 2
whose spectrum is obviously characterized by pairs of integers
Now perturb by
H1 = λ(x2 y + xy 2 ).
We ask what happens to the degenerate n = 1 subspace. So first we compute the
matrix elements hnk|H1 |nli. Here, n = 1 and k, l label the degenerate states.
Before continuing, we note that in the one-dimensional harmonic oscillator,
r
h̄
x= (a + a† ),
2mω
whence
r
h̄
x |0i = |1i
2mω
h̄ h̄ √
x2 |0i = (a + a† ) |1i = (|0i + 2 |2i)
2mω
r 2mω
h̄ √
x |1i = (|0i + 2 |2i)
2mω
h̄ √
x2 |1i = (3 |1i + 6 |3i).
2mω
Having invested this work, we can start bashing matrix elements:
So the matrix elements of H1 in our degenerate block all vanish, and thus
the degeneracy is not broken to first order in perturbation theory.
12
Tony Zhang 5 February 21, 2017 (recitation)
(2)
X (H1 )nl,p (H1 )p,nk
Ml,k = (0) (0)
p6=n En − Ep
(2)
X (H1 )10,px py (H1 )px py ,10
M10,10 =
h̄ω(1 − px − py )
px +py 6=1
But
whence the only px , py that enter into the sum are (11, 31, 00, 22, 02, 20). Then
a little bashing tells us that
(2) 23 λ2 h̄2
M10,10 = − .
12 m3 ω 4
(2)
It turns out that M01,01 has the same value, by symmetry under coordinate
exchange of x and y.
It turns out that
λ2 h̄2
(2) 23 20
M =− .
12m3 ω 4 20 23
13
Tony Zhang
Part II
14
Tony Zhang 6 February 22, 2017 (recitation)
p2 1 p4
∂ψ
ih̄ = mc2 + − + . . . ψ.
∂t 2m 8 m3 c2
But this equation doesn’t treat time and space on the same footing, which is
bad in relativity. We want Lorentz invariance.
But what if we square the equation?
2
∂ ∂
ih̄ ψ = H ih̄ ψ = H 2ψ (6.1)
∂t ∂t
∂2
−h̄2 ψ = (−h̄2 c2 ∇2 + m2 c4 )ψ
∂t2
or
∂2
h̄2 − c2 ∇2 + m2 c4 ψ = 0. (6.2)
∂t2
This equation is the Klein-Gordon equation. It’s nice! We recognize the
d’Alembertian operator, which is Lorentz invariant. But... there’s no way to
incorporate spin. (What if ψ has two components, one for spin up, one for down?
Then the two component equations are totally decoupled, which is unphysical.)
In fact, this equation describes spinless particles, like pions.
OK, but we like our “squared” equation 6.1. So postulate a Hamiltonian like
HD = cαi pi + mc2 β
15
Tony Zhang 6 February 22, 2017 (recitation)
where the three αi and the β are Hermitian matrices. If we require anticommu-
tation relations {αi , αj } = 2δ ij and {αi , β} = 0 and β 2 = 1, we actually satisfy
H 2 = p2 c2 + m2 c4 .
The anticommutation relations turn out to force the matrices to be 4 × 4.
One possible choice is β = diag(1, 1, −1, −1) and
0 ~σ
α~=
~σ 0
in block form.
Then we get the Dirac equation:
∂ψ
ih̄ = −h̄c(αi ∂i )ψ + mc2 ψ (6.3)
∂t
where ψ is now a four-component vector (actually a spinor, which is different
from a four-vector). The Dirac equation describes relativistic spin- 12 particles.
Now to look for stationary states. We have HD ψ(~x) = Eψ(~x). The solution
~
turns out to be ψ(~x) = eik·~x ξ where ξ is some spinor. Then
Since Tr α
~ = Tr β = 0, there are two positive E and two negative E.
Plotting E against p = h̄k, we find two degenerate branches. The top
corresponds to the elctron, the bottom, the positron, which just pops out.
But there’s no ground state, in the sense that if we go to high momentum,
energies get indefinitely low. How do we deal with that? We postulate that all
the negative energy levels are filled by a “Fermi sea” wait what.
16
Tony Zhang 7 February 23, 2016
17
Tony Zhang 7 February 23, 2016
~ field is
whence the potential energy produced by subjecting this thing to a B
~ = geh̄ ~
−µ
~ ·B ~σ · B. (7.4)
4me
Now the Dirac equation predicts that g = 2, a fact that has been experimentally
verified. But it turns out we don’t need such a large hammer to get that result.
Hψ = Eψ
p2
ψ = Eψ
2m
We’d like to describe spin. So replace ψ with a two-component spinor χ and
write
p2
I2 χ = Eχ.
2m
How do we justify this? To couple spin, we might want to replace p~ 7→ ~σ · p~.
Using the fact that
we get (~σ · p~)(~σ · p~) = p2 I2 , where we’re using the fact that p~ × p~ = 0.
So now we can equivalently write
18
Tony Zhang 7 February 23, 2016
19
Tony Zhang 7 February 23, 2016
and see that we can use the third term as a relativistic Hamiltonian perturbation.
In this case, we have p4 = p2 · p2 .
Dirac instead decided to go with the square root in Equation 7.8. So we look
for coefficients αi and β
p2 c2 + m2 c4 = (cαi pi + βmc2 )2
αi2 = β 2 = 1
p2 p4 1 1 dV ~ ~ h̄2
H= +V − 3 2
+ 2 2
S · L+ 2 c2
∇2 V (7.10)
2m 8m c
| {z } | {z } | 2m c r
{zdr } |8m {z }
H0 δHrel δHspin-orbit δHDarwin
In the past, we wrote λ δH for our perturbations. What’s λ here? It’ll come
out in a moment.
Let’s talk about orders of magnitude.
e2
hH0 i ∼ ∼ α2 mc2
a0
p4
hδHrel i m3 c2 p2
= p2
= = α2
hH0 i (mc)2
2m
δHspin-orbit e h̄2 1 2
= 2 2 3 e2 = α 2
hH0 i m c a0 a
0
δHDarwin
= α2
hH0 i
20
Tony Zhang 8 February 27, 2017 (recitation)
You may recall that the Dirac equation yields solutions for electrons and
positrons (which have negative E). But we only care about electrons for now.
So define Es = E − mc2 as the energy shift of interest.
Using the second equation, we write
1
Φ= c(~σ · p~)χ
mc2
+E−V
1
= c(~σ · p~)χ
2mc2 + Es − V
1 Es − V
≈ 1− c(~σ · p~)χ
2mc2 2mc2
21
Tony Zhang 8 February 27, 2017 (recitation)
Taking some corrections gives us the fine structure correction to the Hamil-
tonian.
22
Tony Zhang 9 February 28, 2017
How do we interpret the Darwin term? It accounts for the fact that the
h̄
electron behaves like a little sphere with the size of its Compton wavelength me .
Let’s see how that works.
The potential felt by the particle isn’t V (r) anymore. We need to average
over the entire sphere:
Z
Ṽ (r) = V (r + ρ)f (ρ) dρ (9.2)
R
where f (ρ) gives a normalized “mass density”: f (ρ) dρ = 1. If f (ρ) = δ(ρ),
we recover Ṽ = V .
So we expand with a Taylor series:
X 1X
V (r + ρ) = V (r) + (∂i V )(r)ρi + (∂i ∂j V )(r)ρi ρj + . . . (9.3)
i
2 i,j
23
Tony Zhang 9 February 28, 2017
Clearly, the zeroth-order term factors nicely and normalization kicks in. Now
assume f is spherically symmetric. Then by symmetry, the first-order term
vanishes. Moreover, the second-order term does as well unless i = j:
Z
1X 2
Ṽ (r) = V (r) + (∂i V )(r) ρ2i f (ρ) d3 ρ + . . .
2 i
Z
1
= V (r) + (∇2 V )(r) ρ2 f (ρ) d3 ρ.
6
h̄2
1
Ṽ (r) = V (r) + ∇2 V . (9.6)
10 m2 c2
1
This correction is very close to the actual Darwin term (which has prefactor 8
1
instead of 10 ).
(1) 1
En,rel = − hp2 ψnlm |p2 ψnlm i .
8m3 c2
p2 ψ = (E (0) − V )2mψ,
whence
(1) 1
En,rel = − h(En(0) − V )ψ|(En(0) − V )ψi
2mc2
1
=− hψ|(En2 − 2En V + V 2 )|ψi
2mc2
1
=− [(En(0) )2 − 2En(0) hV inlm + hV 2 inlm ]
2mc2
24
Tony Zhang 9 February 28, 2017
Question 9.2. Why couldn’t we have applied p2 twice on one side instead of
invoking Hermiticity and putting one p2 on each side?
Remark 9.4 (Virial theoerm mnemonic). Imagine the En < 0. The kinetic
energy must counteract this binding energy, so K = hT i = −En > 0. Then
hV i = En − hT i = 2En .
We computed
1 4n
hr−2 i = = (En(0) )2 (9.9)
a20 n3 (` + 21 ) l + 12
on a previous pset.
So we have
(0)
(En )2
(1) 4n 1 4 2 1 4n
En,rel = − − 3 = − α mc − 3 (9.10)
2mc2 ` + 21 8 n4 ` + 21
Now this result was derived in the uncoupled basis |n`m` ms i. But it only
depends on n and `. Therefore, linear combinations of state with the same n
and ` experience the same relativistic energy shift.
So the result is also valid in the coupled basis |n`jmj i.
~ ·L
Using 2S ~ = J 2 − S 2 − L2 , and the known result of hr−3 i, we get
(0)
(1) (En )2 n(j(j + 1) − `(` + 1) − 43 )
En,so =
m2 c2 `(` + 12 )(` + 1)
25
Tony Zhang 9 February 28, 2017
1
Joke. If you want to find the expectation value of r3 and you have to go to the
Laguerre polynomials, you’re finished.
Finally, adding the two energy shifts, we get the total shift of the terms
we’ve considered today:
This result gives the fine-structure correction for ` 6= 0 states, since they have no
Darwin shift. But it’s valid even for ` = 0 states as well, despite the spin-orbit
term being wrong! Indeed, the incorrect spin-orbit term in the ` → 0 limit
exactly compensates for the shift from the Darwin term that we didn’t explicitly
add in.
Yay, so we have a nice formula that depends on j and `. Are we done? Not
quite. Because `⊗ 12 = (`+ 12 )⊕(`− 12 ), we always have ` = j ± 12 . Plugging these
values into Equation 9.11, we get the same expression both times. Therefore, we
can write the grand formula for the fine structure energy shift of hydrogen:
(0)
(En )2
(1) 4n 4 2 1 n 3
Efs =− − 3 = −α mc − . (9.12)
2mc2 j + 21 2n4 j + 1
2
4
26
Tony Zhang 10 March 1, 2017 (recitation)
HD Ψ = EΨ,
α · p~ + βmc2 + V.
HD = c~
(~σ · p~)(~σ · ∇V ) = σ i pi σ j ∂j V
= (δ ij + iεijk σ k )pi ∂j V
p · ∇V ) + iεijk pi (∂j V )σ k
= (~
pi ∂j V = ∂j V pi + [pi , ∂j V ] = ∂j V pi − ih̄∂i ∂j V.
Now assume a central potential, since we’re trying to get at the relativistic
correction for hydrogen. Then
∂r ri
∂i V = V 0 (r) = V 0 (r)
∂ri r
so that
V 0 (r) j k
(~σ · p~)(~σ · ∇V ) = p~ · ∇V − iεijk ri p σ
r
V 0 (r) ~
= p~ · ∇V − i L · ~σ
r
27
Tony Zhang 10 March 1, 2017 (recitation)
1 V 0 (r) ~ ~ e2 ~ · S.
~
Hso = L · S = L
2m2 c2 r 2m2 c2 r4
Ψ† (x)Ψ(x) d3 x.
The integral of this quantity is unity, which is obviously conserved. The integral
of χ† χ, however, isn’t necessarily conserved.
But we can also write
Z Z
Ψ† Ψd3 r = (χ† χ + Φ† Φ)d3 r
Z
3 † 1 †
' d r χ χ+ ((~σ · p~)χ) (~σ · p~)χ
4m2 c2
2
Z
3 † † p
= d r χ χ+χ χ
4m2 c2
p2
Z
= χ† 1 + χ d3 r
4m2 c2
h̄2
HD = ∇2 V.
8m2 c2
28
Tony Zhang
Part III
29
Tony Zhang 11 March 2, 2017
11 March 2, 2017
11.1 WKB; the semiclassical approximation
Today, we look at the Wentzel-Kramers-Brillouin, or WKB, approximation.
This approximation looks at the limit when quantum effects get small. There
are two ways to quantify that:
Here S(x, t) is real with dimensions of action. ρ(x, t) is just the probability
density |Ψ(x, t)|2 .
How do we interpret this phase? We recall the probability current:
h̄
J~ = =(Ψ∗ ∇Ψ).
m
Let’s write it in terms of ρ and S.
Take the gradient of Ψ:
1 ∇ρ iS √ i iS
∇Ψ = √ e h̄ + ρ ∇Se h̄
2 ρ h̄
whence
1 i
Ψ∗ ∇Ψ = ∇ρ + ρ∇S
2 h̄
and
∇S
J~ = ρ . (11.1)
m
Now recall from classical electrodynamics that
p~
J~ = ρ~v = ρ ,
m
so we think of ∇S ∼= p~ as some sort of momentum. Admittedly, this equivalence
is vague, but for a free particle, it makes sense:
~·~
p x−Et
Ψ(x, t) = ei( h̄ )
30
Tony Zhang 11 March 2, 2017
h̄2 00
− ψ + V (x)ψ = Eψ.
2m
Reorganize to define a local notion of “momentum”:
iS d2 iS
p2 (x)e h̄ = −h̄2 (e h̄ )
dx2
d iS 0 iS
= −h̄2 e h̄
dx h̄
00
(S 0 )2 iS
iS iS
= −h̄2 e h̄ − 2 e h̄
h̄ h̄
whence we get the following:
31
Tony Zhang 11 March 2, 2017
The first order term gives 2S00 S10 = iS000 . We can rearrange:
i S000 i ±p0 i p0
S10 = = =
2 S00 2 ±p 2p
A general solution is just a superposition of the two solutions we get from taking
either plus or minus. Depending on whether E > V (x) (classically allowed) or
otherwise (classically forbidden),
i x i x
Z Z
A B
ψ(x) = p exp + p(x0 ) dx0 + p exp − p(x0 ) dx0
p(x) h̄ x0 p(x) h̄ x0
(11.6)
Z x Z x
A 1 0 0 B 1 0 0
ψ(x) = p exp + κ(x ) dx + p exp − κ(x ) dx
κ(x) h̄ x0 κ(x) h̄ x0
(11.7)
The coefficients A and B parameterize our solution family. How valid are these
approximations?
32
Tony Zhang 11 March 2, 2017
11.4 Validity
Because we have a power series expansion in h̄ in Equation 11.4, we expect
it the first-order term to be smaller than the zeroth-order one. Therefore, we
expect:
2πh̄
But we recognize the de Broglie wavelength λ = p , whence, ignoring constant
factors,
λ(x) dp |p|.
(11.8)
dx
whence
dλ
λ λ (11.9)
dx
These two results show that local momentum and de Broglie wavelength
change are basically constant over the length scale of a de Broglie wavelength.
That is, the amount they change is much less than their values.
33
Tony Zhang 11 March 2, 2017
The connection formula says that the solutions in the two regimes take
the form
Z a Z a
2A 1 π B 1 π
p cos p(x0 ) dx0 − −p sin p(x0 ) dx0 − xa
p(x) h̄ x 4 p(x) h̄ x 4
(11.10)
Z x Z x
A 1 B 1
p exp − κ(x0 ) dx0 +p exp κ(x0 ) dx0 xa
κ(x) h̄ a κ(x) h̄ a
(11.11)
These connect at a.
Look at an example first. Suppose our potential is infinite for x ≤ 0, and
grows linearly-ish for x > 0. Moreover, suppose V (a) = E, with x > a classically
forbidden.
The WKB approximation in the classically allowed region, enforcing boundary
conditions at the origin, is:
Z x
1 1
ψ(x) = p sin p(x0 ) dx0
p(x) h̄ 0
| {z }
φ(x)
1 a
Z Z a
π 1 π
φ(x) = p(x0 ) dx0 − − p(x0 ) dx0 −
h̄ 4 h̄ x 4
| 0 {z } | {z }
∆ ξ(x)
Joke. We’re feeling generous today, so we add and subtract whatever we want!
Then
1
ψ(x) = p sin φ
p(x)
1
=p sin(∆ − ξ(x))
p(x)
1 1
=p sin ∆ cos ξ − p cos ∆ sin ξ
p(x) p(x)
34
Tony Zhang 12 March 6, 2017 (recitation)
mZ+2 c2 = mZ c2 + mα c2 + E
We’ll use the WKB approximation here. Generally r1 is really tiny, so the
potential barrier is tall and wide. Then consider an α particle inside the barrior,
with energy E > 0 to allow tunneling. Let r2 denote the turning point, so that
2Ze2
= E.
r2
Since the barrier is tall and wide, we can derive a transmission coefficient
T ∼ e−γ with
s
1 r2 1 4me2 Z r2 r2
Z Z r
0 0
γ= κ(x ) dx = − 1 dr
h̄ r1 h̄ r2 r1 r
√ r r2
2mE p r
= r(r2 − r) + r2 sin−1
h̄ r2 r=r1
35
Tony Zhang 13 March 7, 2017
13 March 7, 2017
First: notation change. We use k(x) instead of p(x), where p = h̄k. Therefore,
we write
2m
k 2 (x) = (E − V (x))
h̄2
2m
κ2 (x) = 2 (V (x) − E)
h̄
Then the condition |h̄p0 | |p2 | becomes |k 0 | |k 2 |, and the WKB exponents
become nicer. The probability density and current become nicer too.
For a WKB wavefunction of the form
Z x
A 0 0
Ψ(x) = p exp i k(x ) dx ,
k(x) a
we would have
|A|2
ρ=
k(x)
and probability current
h̄ h̄
J= =(Ψ∗ Ψ0 ) ' |A|2
m m
We write down the connection formulae. If a is a turning point from allowed
to forbidden,
Ra Ra
√2A cos x k(x0 ) dx0 − π4 − √B sin x k(x0 ) dx0 − π4
x<a
k(x) k(x)
ψ(x) = Rx x
√ A
exp − a κ(x0 ) dx0 + √ B
exp a κ(x0 ) dx0
R
x>a
κ(x) κ(x)
(13.1)
Similarly, from forbidden to allowed at b:
R R
√ A exp − xb κ(x0 ) dx0 + √ B exp xb κ(x0 ) dx0 x<b
κ(x) κ(x)
ψ(x) =
√2A cos x k(x0 ) dx0 − π − √B sin x k(x0 ) dx0 − π
R R
b 4 b 4 x>b
k(x) k(x)
(13.2)
36
Tony Zhang 13 March 7, 2017
h̄2 00
− ψ + (V (x) − E)ψ = 0
2m
becomes
h̄2 00
− ψ + g(x − a)ψ = 0.
2m
But we don’t like dimensionful quantities, so let’s get rid of them. We can get a
characteristic length scale
2 13
h̄
L=
mg
h̄2
using mL2 = gL, both sides of which have dimensions of energy.
Now scale x as 31
2mg
u= (x − a) = η(x − a)
h̄2
where we define η. Then we get Airy’s differential equation
d2 ψ
− uψ = 0, (13.8)
du2
whose solutions are linear combinations of the Airy functions, cousins to the
Bessel functions. Asymptotically, the Airy functions look like
1
(
√1
|u|− 4 e−ζ u1
Ai(u) ' 21 π − 1 (13.9)
√ |u| 4 cos ζ − π
π 4 u0
1
(
√1 |u|− 4 eζ u0
π
Bi(u) ' 1 − 1 π
(13.10)
− √π |u| 4 sin ζ − 4 u −1
3
where ζ = 32 |u| 2 .
Remark 13.1. Whoever determined these asymptotic forms of the Airy func-
tions have really done a lot of the work for us. Near the turning point, the
solutions are Airy functions Ai and Bi, and it just so happens that they take
WKB form asymptotically!
1 1
To see: We have u ∼ (V − E) ∼ k 2 , whence |u|− 4 ∼ k − 2 . Similarly, the
3
exponentials have exponents ζ, √
which go like u 2 . But the exponents in the
WKB solutions are integrals of x (using our linearized potential), giving us
our 32 powers.
Remark 13.2. Consider the asymptotic form of Ai:
1 2
3
ψ(u) = 1 e− 3 u 2 .
u 4
37
Tony Zhang 13 March 7, 2017
Now we write:
k 2 = η 3 (a − x) = −η 2 u = η 2 |u| u<0 (13.11)
2 3 2
κ = η (x − a) = η u u>0 (13.12)
We’re now in a position to ask: how good are the Airy asymptotic forms as
approximations to the wavefunctions? Well, we want |k 0 | |k 2 |.
3 1
Question 13.3. Show that this condition is equivalent to |u| 2 2
, whence
|u| 0.63.
Our program now is to choose coefficients for Equations 13.4 and 13.5 that
make them match up asymptotically with some linear combination of Ai and Bi.
Evaluate integrals near the turning point using the linearized potential
Z x Z x
0 0 3 1 2 3
κ(x ) dx = η 2 (x0 − a) 2 dx0 = |u| 2 = ζ (13.13)
3
Za a a
Now we rewrite the solutions away from the turning point (Equations 13.4
and 13.5) as
1
A|u|− 4 −ζ B 1
u0 ψ(x) = √ e + √ |u|− 4 eζ
π π
' 2A Ai(u) + B Bi(u) (13.15)
− 14 −iζ
|u| e 1
u0 ψ(x) = C √ eiζ + D √ |u|− 4
π π
iπ iπ
iπ iπ
' Ce 4 + De 4 Ai(u) + iDe− 4 − iCe 4 Bi(u)
−
(13.16)
38
Tony Zhang 13 March 7, 2017
13.3 Tunneling
Because *mumble mumble arrows*, in a potential barrier in a tunneling situation,
we can assume that with scattering to the right, with incident, reflected, and
transmitted amplitudes A, B, F , the wavefunction is almost completely decaying.
Then the tunneling probability is just the ratio of probability fluxes
|F |2
T =
|A|2
h̄
(where we’ve cancelled factors of m ).
But WKB tells us that this quantity is just the amount of decay introduced
by the exponential decay:
T = e−2Θ
where Z b
Θ= κ(x0 ) dx0
a
39
Tony Zhang 14 March 8, 2017 (recitation)
for a x b, where
1 b
Z
θ= κ dx0
h̄ a
Remember our expectation that in the forbidden region, the wavefunction is
mostly decaying? We’ll check that C D to verify.
Indeed, connection gives
1 −θ
D= Fe C = −iF eθ
2
whence D C by a factor of e2θ , which incidentally will scale as tunneling
lifetime. We really don’t have a right to keep D, (author’s sketchy note: since
the correction it provides is smaller than the O(h̄) corrections we drop in making
the WKB approximation?) so basically we assume that the wavefunction is
purely exponentially decaying.
Another connection into the region left of the barrier will give |A| = |B| = |C|,
whence
|F | |F |
= = e−θ
|A| |C|
and
|B|
= 1.
|A|
The transmission probability is therefore
|F |2 |B|2
T = = e−2θ R= =1
|A|2 |A|2
They don’t sum to 1 because of approximation errors.
40
Tony Zhang
Part IV
Time-dependent perturbation
theory
41
Tony Zhang 15 March 9, 2017
15 March 9, 2017
15.1 Time-dependent perturbation theory
Today we take up time-dependent perturbation theory. The setup is
simple. Given a known, time-independent H (0) , we want to understand
AH = U † AS U
and define
iH (0) t
|Ψ̃(t)i = U † |Ψ(t)i = e+ h̄ |Ψ(t)i . (15.1)
(0)
We’re “bringing |Ψ(t)i to rest” with respect to H .
We’d like a time-dependent Schrödinger equation for |Ψ̃(t)i. Start with the
familiar one:
ih̄∂t |Ψ(t)i = (H (0) + δH(t)) |Ψ(t)i
Then
†
ih̄∂t |Ψ̃(t)i = ih̄∂t (UH 0
|Ψ(t)i)
= ih̄(∂t U † ) |Ψ(t)i + ih̄U † ∂t |Ψ(t)i
iH (0) t
= −H (0) |Ψ(t)i + e h̄ (H (0) + δH(t)) |Ψ(t)i
= −H (0) |Ψ(t)i + U † (H (0) + δH(t))U |Ψ̃(t)i
= (U † δH(t) U ) |Ψ̃(t)i .
42
Tony Zhang 15 March 9, 2017
so that
∂
ih̄ |Ψ̃(t)i = δH(t)
f |Ψ(t)i . (15.3)
∂t
So now we have
Once we solve this problem, we can add in the H (0) time dependence simply as
iH (0) t
|Ψ(t)i = e− h̄ |Ψ̃(t)i .
for unknown coefficient functions cn (t). Then we can bop this equation with
UH (0) to get X iEn t
|Ψ(t)i = cn (t)e− h̄ |ni . (15.5)
n
This equation should make you happy! If the cn (t) were constant, we recover
ordinary time-evolution of |Ψ(t)i under H (0) .
Now plugging into our Schrödinger equation,
X X X XX
ih̄ċm (t) |mi = cn |mi hm| δH
f |ni = |mi hm|δH|ni
f cn (t)
m n m m n
Problem 15.2. Let’s start with a two-state system with stationary states
|ai , |bi. with respective energies Ea , Eb . Define a charactristic frequency
Ea − Eb
ω0 = .
h̄
Remember how we said perturbations shouldn’t last long? We’ll take the
shortest possible perturbation: a delta function! We have δH = U δ(t) for
Hermitian U with Uaa = Ubb = 0 and Uab = α.
Suppose the system is in |ai for t = −∞. What is the probability we find it
in |bi at t = ∞?
43
Tony Zhang 15 March 9, 2017
Start by considering
ca (t) = 1 cb (t) = 0
or
f (x)δ(x) = f (0)δ(x).
The first step is relatively kosher, since eiω0 t is continuous. But in general we
have no idea whether the ca and cb are continuous. Indeed, we really don’t
expect them to be. So it’s sketchy to make the second step.
Therefore, we write
Then
iα |α|2
c̈a = − ċb = − 2 2 ca (t)
h̄t0 h̄ t0
and something similar for cb , whence
|α|t |α|t
ca = β0 cos + β1 sin
h̄t0 h̄t0
44
Tony Zhang 15 March 9, 2017
|α|t
ca (t) = cos
h̄t0
i|α| |α|t
cb (t) = − sin
α h̄t0
So at t0 , we have
|α|
ca (t) = cos
h̄
i|α| |α|
cb (t) = − sin
α h̄
All t0 dependence has now dropped out, so taking the limit of regularizer t0 → 0
is trivial, and we get
|α|
Pr(b; t = 0+ ) = sin2
h̄
Remark 15.3. One might argue that introducing the step function regulation
is unphysical. On the contrary, the regulation is totally the right thing to do;
the problem itself was unphysical!
45
Tony Zhang 16 March 13, 2017 (recitation)
Let the transition time be ∆t = ε → 0. If it’s “short enough”, the state will
have no time to change, and will remain the same. Let’s figure out what “short
enough” is.
As always, we have the time-dependent Schrödinger equation:
∂ |ψi
ih̄ = H(t)ψ(t).
∂t
Integrating,
Z 1 ε
1 1 2
ih̄ ψ ε −ψ − ε = H(t0 )ψ(t0 ) dt0 ∼ ∆E ∆T ψ(0).
2 2 − 21 ε
We want the left hand side to be basically 0, so the condition for our approxi-
mation holding is for ∆E ∆t h̄.
One can derive this relation more rigorously by actually finding an expression
for the energy uncertainty. But the intuition is simple: the relative phase
differences in quantum state time evolution grow as exp( i∆E t
h̄ ).
46
Tony Zhang 16 March 13, 2017 (recitation)
the ejected electron has average energy 5.7 keV, which translates to a velocity
of v = 0.15c. So the electron leaves within ∆t = av0 = 1.2 × 10−18 s. The
typical energy in a hydrogen atom is 10 eV, so we have ∆Eh̄
= 6.4 × 10−17 s, so
∆E∆t h̄, and we can use the instantaneous approximation.
If the tritium atom began in the ground state, we could figure out the
time-evolution of the helium ion (another hydrogenic system) by assuming the
helium ion starts in the hydrogen ground state
1 r
ψ100 (r) = p e− a0 ,
πa30
which we would decompose into helium ion states, which look like the hydrogen
ones, with a0 7→ 12 a0 . We’d evolve each component separately, as usual.
47
Tony Zhang 17 March 15, 2017 (recitation-cum-lecture)
∂ |Ψ̃i f |Ψ̃i
ih̄ = δH (17.3)
∂t
where (0) t iH (0) t
f = e iHh̄
δH δHe− h̄ . (17.4)
with
Em − En
ωmn = . (17.7)
h̄
Finally, considering a perturbative expansion
|Ψ̃(t)i = |Ψ̃(0)i + |Ψ̃(1) (t)i + . . . , (17.8)
we find the first order correction is
Z t f 0)
δH(t
|Ψ̃(1) (t)i = |Ψ(0)i dt0 . (17.9)
0 ih̄
= |hm|Ψ̃(1) (t)i|2
48
Tony Zhang 17 March 15, 2017 (recitation-cum-lecture)
c(1)
m (t) = hm|Ψ̃
(1)
(t)i
* Z +
t δH(tf 0) X
= m c(0)
n n
0 ih̄ n
X tZ
0 δHmn
= eiωmn t c(0) dt0 (17.11)
n 0 ih̄ n
49
Tony Zhang 17 March 15, 2017 (recitation-cum-lecture)
4|Vf i |2 sin2 21 ωf i t0
2
(1)
Pr (t0 ) = cf (t0 ) = . (17.13)
f ←i (Ef − Ei )2
ωf i t0 1.
That is, a smaller energy split makes this result valid for longer.
Now consider what happens if our spectrum is continuous (e.g. the scattering
states of hydrogen). It turns out we’ll be able to apply the same logic to such
states as well; transition probabilities are not transition probability densities,
etc.
Let’s consider helium (Z = 2, with two electrons). Suppose that the two
electrons are in hydrogenic states with principal quantum numbers n1 , n2 . The
total energy of the system is then
2 1 1 1 1
En1 ,n2 = −(13.6 eV )Z + = −54.4 eV + (17.15)
| {z } n21 n22 n21 n22
Ry
So it seems like we have a discrete spectrum until we get to energy zero. But
that’s not true. Indeed, we have E∞,1 = −54 eV; therefore, our continuum
actually starts here. If we’re in a bound state, like E2,2 , with greater energy,
there is actually a probability we transition into a state with a free electron;
this is the Auger effect.
50
Tony Zhang 18 March 16, 2017
we must have
L~
k = (nx , ny , nz )
2π
be an integer vector. The number of states within a volume element in ~n space
is thus 3
L
∆N = dnx dny dnz = d3 k.
2π
d3 k = k 2 dk dΩ
where dΩ = sin θ dθ dφ is a solid angle element. But recall that plane wave
energies are given by
h̄2 k 2
E= ,
2m
so that
km
d3 k = 2 dE dΩ
h̄
and 3
L m
∆N = k dΩ dE
2π h̄2
| {z }
ρ(E)
51
Tony Zhang 18 March 16, 2017
0.8
0.6
0.4
0.2
0
−4π −3π −2π −π 0 π 2π 3π 4π
2
Figure 1: The square of the sinc function sinc2 z = sinz2 z . The central lobe
captures 90% of the mass. Within 2π of the origin lies 95% of the mass; within
10π, 99%.
where we’ve defined a state density per unit energy in solid angle dΩ.
Therefore, the probability of transitioning into an energy eigenstate with
energy Ef ∈ F is Z
Pr (t0 ) = Pr (t0 )ρ(Ef ) dEf .
F ←i F f ←i
Notice the sinc squared. Looking at Figure 1, the main contribution to such
an integral comes from the central lobe of the sinc squared. Indeed, we will
capture 90% of the integral of sinc2 z in the first lobe |z| < π.
We’re in the first lobe when |ωf i t0 | < 2π, or equivalently,
2πh̄ 2πh̄
Ei − < Ef < Ei + .
t0 t0
Changing to integration variable
1
u= ωf i t0 ,
2
52
Tony Zhang 18 March 16, 2017
∆t0
If 2h̄ π, this integral is basically the full integral over all u:
Z ∞
1 1
I ≈ h̄t0 sinc2 u du = πh̄t0 .
2 −∞ 2
2π
W = |Vf i |2 ρ(Ef = Ei ) . (18.6)
h̄
This transition rate tells us the probability per unit time that we transition into
a state with energy Ei ± ∆ where ∆ 2πh̄ t0 .
3
with
0
t<0
0
δH = 2H cos ωt 0 < t < t0 . (18.8)
0 t > t0
the likelihood of going far from Ei is negligible, due to the sinc2 u supression. Assuming a
transition occurs, about 90% of the time, we’ll be within 2πh̄
t
of Ei .
0
53
Tony Zhang 18 March 16, 2017
54
Tony Zhang 19 March 21, 2017
What follows will look much like the constant transitions case we worked out.
Suppose we’re interested in the probability of transition into any state within
some small ∆ of Ei + h̄ω. So we integrate, making the same approximations as
in the constant transitions case:
|Hf0 i |2 4 sin2 21 (ωf i − ω)t0
Z Ei +h̄ω+∆
Pr = ρ(Ei + h̄ω) dEf
f ←i h̄2 Ei +h̄ω−∆ (ωf i − ω)2
Z ∆t
|Hf0 i |2
0
2h̄ 4 sin2 u 2h̄
= 2 ρ(Ei + h̄ω) du
h̄ ∆t
− 2h̄0 u2 t42 t0
0
∆t0
2|Hf0 i |2
Z 2h̄
= t0 ρ(Ei + h̄ω) sinc2 u du
h̄ −
∆t0
2h̄
Taking the limits of the integral to infinity and dividing out t0 , we get our
transition rate
2π 0 2
Γf ←i = |H | ρ(Ei + h̄ω) (19.1)
h̄ f i
55
Tony Zhang 19 March 21, 2017
δH = −eΦ(t)
Φ = −E(t)z.
Therefore,
δH = 2 eE0 r cos θ cos ωt.
| {z }
H0
This integral is not so easy. For example, we normally don’t have φ0 depen-
dence; however, there’s a stealthy dependence here in θ00 . Let’s handle that
term. We have
~ · r̂
|E| cos θ00 = E
= Ex nx + Ey ny + Ez nz
= |E| (sin θ cos φ sin θ0 cos φ0 + sin θ sin φ sin θ0 sin φ0 + cos θ cos θ0 )
cos θ = sin θ sin θ0 cos(φ − φ0 ) + cos θ cos θ0
00
56
Tony Zhang 19 March 21, 2017
Already, the angular dependence pops out. It’s not that surprising: given an
electric field, we expect ejection probability to be concentrated in the direction
of the electric field, with no probability perpendicular.
Omitting the remaining steps of integration (which are now really straight-
forward), we get our desired overlap:
√ ka4 1
hf |H 0 |ii = −32i π(eE0 a) p 0 3 2 a2 )3
cos θ. (19.2)
3
L a0 (1 + k 0
Then
k 2 a50 1
|Hf i |2 = 1024π(eE0 a)2 cos2 θ
L (1 + k 2 a20 )6
3
Now we only need the state density to use Fermi’s Golden Rule:
L3 mh̄2
ρ(E) = sin θ dθ dφ (19.3)
8π 3 k | {z }
dΩ
Finally, we might integrate this rate over the entire sphere to get an ejection
rate. The angular dependence can be integrated as
Z
4
dΩ cos2 θ = π
3
whence
1024 (eE0 a0 )2 ma20 k 3 a30
W = . (19.6)
3 h̄ h̄2 (1 + k 2 a20 )6
Remark 19.1. Two nice integrals to remember:
Z Z
1 1 1 2
2
dΩ cos θ = dΩ sin2 θ = .
4π 3 4π 3
The way to remember: cos2 θ is concentrated at the poles and sin2 θ is concen-
trated around the much larger equatorial region.
57
Tony Zhang 19 March 21, 2017
1. If the electron is in |ai, the photon can be absorbed with some absorption
rate, exciting the electron to |bi.
2. The electron starts in |bi, and we get stimulated emission of a photon.
The electron decays to |ai; one photon goes in, two go out. (Lasers work
like this: you excite a bunch of atoms, then shine a little light on them.
That light gets amplified.)
We already have the tools to analyze these two transitions (i.e. Fermi’s Golden
Rule).
But there’s another transition that’s super important: spontaneous emis-
sion. Spontaneous emission is hard to explain at first, because shouldn’t energy
eigenstates be stationary? The way to think about it is that there are vacuum
fluctuations of the EM field that perturb the system ever so slightly.
58
Tony Zhang 20 March 22, 2017 (recitation)
h̄2 |~k|2
E= .
2m
L3 km
ρ(E) = dΩ (20.1)
(2π)3 h̄2
whence Fermi’s Golden Rule
2π
Γf ←i = ρ(Ef )|hf |δH|ii|2 (20.2)
h̄
gives differential transition rate
kf m
dΓ = |Ṽ (~kf − ~ki )|2 dΩ
(2π)2 h̄3 L3
60
Tony Zhang 21 Apri 4, 2017
21 Apri 4, 2017
We continue our discussion of light and atoms. Today, we will cover Einstein’s
discovery of spontaneous emission and the argument he used to calculate its
rate. Note that this argument is thermodynamic, and does not come from first
principles (i.e. not derived by interpreting spontaneous emission as stimulated
emission by vacuum fluctuations).
1. Ṅa = Ṅb = 0
Nb e−βEb
2. Na = e−βEa
= e−βh̄ωba .
3. Assuming thermal radiation, the energy density in frequency interval dω is
3
h̄ ω dω
U (ω) dω = 2 3 . (21.1)
π c eβh̄ω − 1
where we’ve considered some coefficients Bab and Bba that give the transition
rate.
Then we have
But Bab and Bba are atomic properties, and thus independent of temperature
T . So none of the three factors is zero in general, and we get a contradiction.
This argument is due to Einstein; when he saw this contradiction, he added
a third process: spontaneous emission. We summarize our three pathways
in Table 1.
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Tony Zhang 21 Apri 4, 2017
Now we try our above argument again, this time with spontaneous emission:
whence
Bab = Bba (21.2)
and
A h̄ω 3
= 2 ba3 . (21.3)
Bab π c
Recall that in first-order time-dependent perturbation theory, the symmetric
transition rates are equal. We see that here too. Also, we have a nice way to
get Einstein’s A coefficient, the rate of spontaneous emission.
Remark 21.1. Some people like to say that all emission is stimulated emission.
It’s just that there are vacuum fluctuations in the electromagnetic field that
can stimulate emission, giving what we like to call spontaneous emission. But
it’s inconvenient to actually do calculations about spontaneous emission by
considering vacuum fluctuations and such.
So in the end, paraphrasing Griffiths, spontaneous emission is just stimulated
emission from photons we didn’t put there.
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Tony Zhang 21 Apri 4, 2017
where we’ve found the dipole moment of the atom. Finally, we have
Now
|E|2 E2
UE = = 0 cos2 ωt
8π 2π
whence a time average gives
1 2
hUE it = E .
4π 0
The total time-averaged energy of the electromagnetic field (including the
magnetic field) is then double that:
1 2
hU i = E .
2π 0
Therefore, Z Z
E02 (ω) dω = 2π U (ω) dω.
We’ll use this result right now in our computation of the transition probability.
Now in a thermal bath, there are multiple incoherent perturbations of
differing ω. Incoherence means probabilities add classically:
2 1
|(d~ · ~n)ab |2
2 sin 2 (ωba − ω)t
Z
Pr (t) = 4E0 dω
a←b h̄2 (ωba − ω)2
|(d~ · ~n)ab |2 sin2 21 (ωba − ω)t
Z
= 2π U (ω) dω
h̄2 ωba −ω 2
2
Now we’re in Fermi’s-Golden-Rule land! Again, the sinc is peaked for large t, so
pulling out U (ω) and making a substitution x = 12 (ω − ωba )t, we recognize our
Dirichlet integral:
4π |d~ab · ~n|2
2
= U (ωba )t
h̄2
and get our transition rate:
4π 2 |d~ab · ~n|2
Ra←b = U (ωba ) . (21.4)
h̄2
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Tony Zhang 21 Apri 4, 2017
4π 2 ~ 2
Ra←b = |dab | U (ωba ) . (21.5)
3h̄2
Then we recognize
4π 2 ~ 2
Bab = Bba = |dab | . (21.6)
3h̄2
h̄ω 3
and A = Bab π2 cba3 gives
3
4 ωba
A= |d~ab |2 . (21.7)
3 h̄c3
1
whence we get lifetime τ = A and
Nb (t) = Nb (0)e−t/τ .
Real atoms have multiple relaxation pathways from any given excited state.
The sizes of the various A coefficients thus determine the selection rules, which
tell us which atomic transitions are actually possible in a reasonable amount of
time.
Also, this sort of argument shows that almost any particle, any quantum
system, is unstable in some way. Even protons and neutrons! But some transition
pathways are rather forbidden in the sense that their A coefficients are small.
Question 21.2. On the other hand, electrons are actually stable. Why?
Answer. They don’t have a decay pathway available to them— they’re the
least massive known negatively charged particles.
Last thing: in general, we can find the lifetime of a state by inverting the
total spontaneous emission rate: the sum of all the relevant A coeficients.
64
Tony Zhang 22 April 5, 2017 (recitation)
4 αω 3
A= |hb|~x|ai|2 . (22.1)
3 c2
Now it turns out that A will often be 0 because the matrix element there
vanishes: some transitions are rather forbidden. It would be nice to know if it
does before trying to bash out the integral.
Suppose we’re in hydrogen (or some other rotationally invariant system),
with states |n`mi (ignoring fine structure, spin-orbit coupling, and such). What
sorts of decay are possible?
These two relations between the x sandwich and the y sandwich force upon us
hn0 `0 m0 |x|n`mi = (m0 − m)2 hn0 `0 m0 |x|n`mi. So either m0 − m = ±1 or both
sandwiches vanish.
65
Tony Zhang 22 April 5, 2017 (recitation)
Proof sketch. Using [Li , xj ] from before, find that [L2 , xi ] = 2ih̄(εijk xj Lk −ih̄xi ).
Then use xk Lk = 0.
hn0 `0 m0 |[L2 , [L2 , xi ]]|n`mi = h̄2 (`0 (`0 + 1) − `(` + 1)) hn0 `0 m0 |[L2 , xi ]|n`mi
= h̄4 (`0 (`0 + 1) − `(` + 1))2 hn0 `0 m0 |xi |n`mi
2h̄2 hn0 `0 m0 |(xi L2 + L2 xi )|n`mi = 2h̄4 (`0 (`0 + 1) + `(` + 1)) hn0 `0 m0 |xi |n`mi
= 2h̄4 (`0 (`0 + 1) + `(` + 1)) hn0 `0 m0 |xi |n`mi
Problem 22.3. Show that the total decay rate of a state |n`mi is independent
of m.
66
Tony Zhang
Part V
67
Tony Zhang 23 April 6, 2017
23 April 6, 2017
Today, we begin our unit on the adiabatic approximation.
p2 1
H(p, x; t) = + mω 2 (t)x2 . (23.1)
2m 2
Proposition 23.2
The quantity
H(t)
I(t) = (23.6)
ω(t)
is an adiabatic invariant for the classical harmonic oscillator system.
68
Tony Zhang 23 April 6, 2017
Proof. Compute:
dI ω(t) dH
dt − H dt
dω
=
dt ω2
∂H
ω − H ω̇
= ∂t 2
ω
p2
mω 2 ω̇x2 − ( 2m + 21 mω 2 x2 )ω̇
=
ω2
p2
ω̇ 1
= 2 mω 2 x2 −
ω 2 2m
ω̇
= 2 (V (t) − K(t))
ω
Now
Z t+T
dI 0
I(t + T ) − I(t) = dt
t dt0
t+T
ω̇(t0 )
Z
= 2 (t0 )
(V (t0 ) − K(t0 )) dt0
t ω
Z t+T
ω̇(t)
≈ 2 V (t0 ) − K(t0 ) dt0
ω (t) t
≈0
p2 1
+ mω 2 x2 = E,
2m 2
so the oscillator traces out an ellipse in the clockwise direction. This ellipse has
semiaxes
√
r
2E
a= 2
b = 2mE
mω
2πE
and thus area πab = ω = 2πI. This area is just the contour integral
I
p dx (23.7)
along the phase space trajectory, so it appears that this expression is the “true”
adiabatic invariant: true for any oscillatory motion.
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Tony Zhang 23 April 6, 2017
that energy eigenstates will want to stay in an energy eigenstate under adiabatic
change.
We can motivate some more: for any one-dimensional Hamiltonian with turn-
ing points x1 and x2 for energy E, the WKB approximation gives quantization
condition I
1 1
p(x) dx = 2π n + ,
h̄ 2
suggesting that quantum number n is an adiabatic invariant in the general case,
at least semiclassically.
Even more intuition. Recall that first-order time-dependent perturbation
theory gives Z 2
t 0
iωf i t0 δH f i (t )
f
0
Pr (t) = e dt . (23.8)
f ←i 0 ih̄
For a constant perturbation,
2
1 f 2 t iωf i t0 0
Z
Pr (t) = |δH |
fi e dt
f ←i h̄2 0
1 |eiωf i t |2
= 2 |δHf i |2
h̄ ωf2 i
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Tony Zhang 23 April 6, 2017
so that
ċ(t) |ψ(t)i = −c(t) |ψ̇(t)i . (23.12)
Adjoining with the known instantaneous eigenstate gives
so that
hψ|ψ̇i(t0 ) dt0
Rt
c(t) = c(0)e− 0 . (23.13)
Wait. This quantity looks like it’s real, which is bad. We want it pure imaginary,
so that |Ψi is properly normalized. We check:
Z
hψ|ψ̇i = ψ ∗ ψ̇ dx
Z
d ∗
= (ψ ψ) − ψ̇ ∗ ψ) dx
dt
Z Z
d
= ψ ∗ ψ dx − ψ ψ̇ ∗ dx
dt
| {z }
1
Z ∗
=0− ψ ∗ ψ̇
∗
= − hψ|ψ̇i
whence we have
E(t0 ) dt0 i hψ|ψ̇i dt0
i
Rt Rt
|Ψ(t)i = c(0)e− h̄ 0 e 0 |ψ(t)i . (23.14)
so that
|Ψ(t)i = c(0)eiθ(t) eiγ(t) |ψ(t)i . (23.18)
We call the first phase (accumulated from the energy) the dynamical phase;
the second, the geometric phase or the Berry phase.
71
Tony Zhang 24 April 11, 2017
72
Tony Zhang 25 April 12, 2017 (recitation) TODO TODO TODO TODO
H̃(t/T ) = H(t)
on the interval [0, 1]. To slow down the evolution of H, we would simply take
T → ∞. Assume H̃ has instantaneous eigenstates
Now
Z
1
θn (t) = − En (t0 ) dt0
h̄
1 t
Z
=− Ẽn (t0 /T ) dt0
h̄ 0
T t/T
Z
=− Ẽn (s0 ) ds0
h̄ 0
≡ T θ̃n (t/T )
Now defining
∂
Fkn (s) = hψ̃k | |ψ̃n i ei(γ̃n γ̃k )(s) ,
∂s
73
Tony Zhang 25 April 12, 2017 (recitation) TODO TODO TODO TODO
we rewrite as
XZ t
0
c̃k (t) − c̃k (0) = − Fkn (s0 )eiT (θ̃n −θ̃k )(s ) c̃n (s0 T )ds0
n6=k 0
Define
ĉ(s, T ) = c̃(sT )
so that
XZ t
0
ĉk (s, T ) − ĉk (0, T ) = − Fkn (s0 )eiT (θ̃n −θ̃k )(s ) ĉn (s0 , T ) ds0 .
n6=k 0
Things are looking real good. We have lots of T −1 -prefactors. All the tilde’d
quantities depend on s ∈ [0, 1], so don’t have T -dependence.
d
Further, ĉk is bounded. All we want now is to show that ds ĉk (s, T ) is
bounded. Write:
d X
ĉk (s, T ) = − Fkn (s0 )eiT (θ̃n −θ̃k ) (s0 )ĉn (s0 , T )
ds
n6=k
74
Tony Zhang 26 April 14, 2017
with time-independent constant H12 , the energy level crossing is avoided. The
new energies are given by
r
1
E± (t) = ± |H12 |2 + α2 t2 (26.3)
4
with an minimum energy gap of 2|H12 | at t = 0. We want to find the probability
of switching branches (the probability of a non-adiabatic transition, also
known as diabatic passage).
Assuming without loss of generality that H12 is real, the new instantaneous
eigenstates are precisely those pointed along the unit vector
(H12 , 0, 21 αt)
~n = q . (26.4)
2 + 1 α2 t2
H12 4
But recall that when |H12 | vanishes, we found that states do not flip at all, no
matter how slow you go. So we see that as the energy gap 2|H12 | shrinks, the
adiabatic timescale increases.
Let’s make that more precise. Holding α fixed, we see that the probability
of the non-adiabatic transition from the top branch to the bottom branch goes
to 1 as |H12 | → 0. Conversely, this probability is suppressed for large |H12 |.
In fact, define a timescale t∗ by using the “bounding box” of the hyperbola
(see Figure ??). We have
1
|H12 | = αt∗
2
or
|H12 |
t∗ = 2 ≡ 2τd . (26.5)
α
The quantity τd is a measure of the duration of the change in H.
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Tony Zhang 26 April 14, 2017
ω12 τd 1. (26.8)
h̄
Now rather unrigorously, write T = H and divide by H, so that
h̄ dH
H 2 dt 1.
As a result,
d h̄
dt H(t) 1,
or
d h̄
dt E(t) 1. (26.10)
Suppose we start in state |2i in the infinite past, so A(t = −∞) = 0 and
B(t = −∞) = 1. We want to find B(t = ∞).
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Tony Zhang 26 April 14, 2017
Using either special functions or complex analysis, one can find (as Zener
did) the transision probability: the probability of staying in |2i:
1 t
Z
θn (t) = − En (t0 ) dt0 (26.15)
h̄ 0
Z t
γn (t) = νn (t0 ) dt0 (26.16)
0
where we have
νn (t) = i hψn (t)|ψ̇n (t)i . (26.17)
Berry’s observation was simple, but not realized for a long time. Suppose
now that H depends on N possibly time-dependent coordinates
~
R(t) = {R1 (t), . . . , RN (t)}
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Tony Zhang 26 April 14, 2017
which no longer depends on time explicitly, only implicitly through the path
traced in configuration. In particular, if we evolve the Hamiltonian in the same
way through configuration space, just at different rates, the accumulation of the
geometric phase is the same.
Note that γn (R~i → R ~ f ), which in this form we call Berry’s phase, is
path-dependent. But there is no more time dependence. The N -component
integrand
~ n (R)
A ~ = i hψn (R)|∇
~ ~
r |ψn (R)i
~ (26.20)
is called Berry’s connection. We call it a connection rather than a vector
because it doesn’t quite behave like a vector; it’s like the electrodynamic vector
potential, which has a certain amount of gauge freedom.
Indeed, suppose we define new instantaneous eigenstates
~
~ = e−iβ(R) ~
|ψ̃n (R)i |ψn (R)i (26.21)
So our choice of guage will change the Berry phase. But if we trace a closed
path in configuration space, the phase becomes gauge-invariant.
78
Tony Zhang 27 April 20, 2017
79
Tony Zhang 27 April 20, 2017
~
The curl on the right hand side is sometimes called Berry’s curvature B.
Example 27.1
Consider an electron in a magnetic field
~ = B0~n(t).
B
The Hamiltonian is
H = −~ ~ = µB B0~n · ~σ
µ·B
where we use the Bohr magneton
eh̄
µB = .
2me c
~ is ~n on the unit sphere. Our
Here, the configuration space vector R
instantaneous eigenstates are
~n · ~σ |~ni = |~ni
~n · ~σ |−~ni = − |−~ni
80
Tony Zhang 27 April 20, 2017
Still, it’s not super obvious, for example, whether two protons and an electron
can form a bound state. The answer to this question is actually yes: we can
prove the existence of a bound state, the H2 + ion.
Joke. “Mathematical physicists enjoy doing that kind of thing.”– (talking
about the rigorous proof that no bound state exists with three protons and one
electron)
1 h̄2
M ω 2 a2 ∼ .
2 ma2
Note that we don’t expect nuclear oscillations to be so big. (But if they were,
we’d expect them to affect electron energy levels significantly.) (Yes, this is not
particularly rigorous, but meh.)
As a result,
1 h̄2 m h̄2
ω2 ∼ =
M ma4 M m2 a4
so
m h̄2
r r
m
Evib ∼ h̄ω = = Eelec .
M ma2 M
It makes sense that this energy is smaller. Indeed, nuclear vibration slightly
deforms the electron clouds; this elasticity contributes.
The energy scales are then roughly
r
m m
Eelec : Evib : Erot = 1 : : . (27.7)
M M
So in a typical molecule, these energy scales each differ by two orders of magni-
tude.
We set up a molecular Hamiltonian now. We write
N n
X p2α ~ +
X p2i ~ ~r) + Vee (~r)
H= + Vnn (R) + Ven (R, (27.8)
α=1
2M α i=1
2m
| {z }
~
He (R)
To think about this problem adiabatically, imagine we fix all nuclear degrees
of freedom. With a fixed nuclear skeleton, we solve for the electron wavefunctions.
These will precisely be our instantaneous eigenstates, and our configuration
space will be the nuclear degrees of freedom. Under “slow” vibrations of the
nuclei, the adiabatic theorem tells us that the electrons will stay in instantaneous
eigenstates.
In particular, we solve the Schrödinger equation
!
h̄2 X 2 ~ ~r) + Vee (~r) φ(i) (~r) = Ee(i) (R)φ
~ (i) (~r)
− ∇ri + Ven (R, R R (27.9)
2m i
This equation is still hard and intractible, but it’s much better than using the
full Hamiltonian from above. We can find candidate solutions by making guesses
(eh, this electron probably has a Gaussian-like distribution, parameterized by
some mean and covariance, etc.). If we want to estimate the ground state energy,
we can apply the variational method on our candidate wavefunction families,
finding the choice of parameters that minimize the energy expectation.
But suppose we went beyond even that and found analytic solutions, labeled
by superindex i, which gives the energy levels. Then we know the energies
(i) ~ (i)
Ee (R) and the wavefunctions φR (~r). To get the (approximate) solution for
the entire molecule, we would then write
~ (i) (~r).
X
~ ~r) =
ψ(R, η (i) (R)φ (27.10)
~
R
i
82
Tony Zhang 28 April 24, 2017 (recitation)
where A ~ n is the Berry connection. Why did we restrict the integral to closed
paths? There is gauge freedom here: if we use instantaneous eigenstates
eiβ(R) |ψn (R)i, A~ n changes by ∇R β(R). If we trace a closed path in configuration
space, however, γn becomes gauge-independent.
− sin θ2
0 1 1 0
∇R |+(t)i = r̂ + θ̂ + φ̂
0 2r eiφ cos θ2 r sin θ eiφ sin θ2
Note that the components of the gradient are spinors. Now adjoining h+(t)|
gives us the Berry connection
2 θ
~ + (R) = − 1 sin 2 φ̂ = − 1 tan θ φ̂.
A
r sin θ 2r 2
83
Tony Zhang 28 April 24, 2017 (recitation)
~ + (R) = ∇ × A
~+ = 1 1 1
D ∂θ (Aφ sin θ)r̂ − ∂r (rAφ )θ̂ = − 2 r̂.
r sin θ r 2r
The Berry phase is then
ZZ Z
γ+ = D ~ = −1
~ + (R) · dΣ 1 1
r̂ · r2 dΩ r̂ = − Ω.
2 r2 2
since the latter is the gradient of a function. We therefore get the same curl for
both.
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Tony Zhang 29 April 25, 2017
H = ĤN + Ĥe
X p2
ĤN = α ~
+ VN N (R)
α
2M α
X p2
Ĥe = i ~ ~r) + Vee (~r)
+ VeN (R,
i
2m
where subscript α labels the N nuclei and subscript i labels the n electrons.
The V are the interactions between pairs of particles; we group the interaction
terms based on the types of the particles (i.e. electron or nucleus).
(i)
If we can solve the electronic wavefunctions φR (~r), the entire molecular
wavefunction is then
~ (i) (~r)
X
~ ~r) =
ψ(R, η (i) (R)φ ~
R
i
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Tony Zhang 29 April 25, 2017
~ ~r) = η(R)φ
where ψ(R, ~ ~ (~r). We claim that we can actually write this expectation
R
as
~
hη(R)|H ~
eff |η(R)i
We shall be able to move some terms across the H and do the ~r integral.
Write hHi = hHN ifull + hHe ifull , where the subscripts denote expectations
~ ~r) Hilbert space, so that
on the (R,
Z Z
hHe ifull = d~r dR ~ η ∗ (R)φ
~ ∗R (r)He (η(R)φR (r))
But He commutes with η. To see, note that the kinetic term is a differential
operator in ~r only, so that commutes across η. Further, the potential terms are
multiplicative, so we can harmlessly move them. Therefore,
~ e φR (~r) = η(R)E
He (η(R)φR (r)) = η(R)H ~ e (R)φ
~ R (~r)
and
Z Z
hHe ifull = d~r ~ η ∗ (R)φ
dR ~ ∗R (r)η(R)E
~ e (R)φ
~ R (~r)
Z
= ~ η ∗ (R)
dR ~ Ee (R)
~ η(R)
~
| {z }
∈Heff
Finally, we consider the nuclear kinetic term, the really nontrivial portion.
Indeed, it contains derivatives of R, so we can’t just commute it across η. We
write
2 Z
pα 1 ~ ∗ (~r)pα pα (η(R)φR (~r)) dr dR
= η ∗ (R)φ R
2Mα full 2Mα
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Tony Zhang 29 April 25, 2017
Now we have
φ∗R pα = pα φ∗R − (pα φ∗R )
where every term should be thought of as an operator. Then we get four terms
in our expectation
2 Z
pα 1 ~
= dr dR η ∗ (R)
2Mα full 2Mα
{pα [φ∗R (pα η(R))φR (r) + φ∗R η(R)(pα φR (~r))]
−(pα φ∗R (r)) [(pα η(R))φR + η(R)(pα φR (r))]}
where, as good physicists, we make all the simplifications we know how to make
and give the things we don’t know
R how to deal with a name. We see a 1: good!
But we see a Berry-like thing: φ∗ (pα φ) dr. Indeed, it’s a Berry connection
Z Z
~ = ih̄ φ∗R (r)∇R φR (r) dr = − φ∗R (r)pα φR (r) dr
Aα (R) (29.5)
α
~ configuration space.
over the R
Continue:
p2α
Z
1 ~
= dR η ∗ (R)
2Mα full 2Mα
2
pα η(R) − pα (η(R)Aα (R))
Z
2
−Aα (R)pα η(R) + h̄2 η(R) |∇R φ∗R (r)| dr
where
X h̄2 Z 2
X A2
α
U (R) = VN N (R) + Ee (R) + |∇R φR (r)| dr − . (29.8)
α
2M α α
2M α
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Tony Zhang 29 April 25, 2017
While our Heff is conceptually nice, it’s still real hard to solve. In practice,
people often start with the naive Heff , bringing in the full effective Hamiltonian
if they need more accurate answers.
h̄2 ∇2
1 1
hHe i = ψtrial − − e2 + ψ trial = Ee (R) (29.13)
2m r1 r2
Now the total potential is just VN N (R) + Ee (R) which gives a minimum
energy of −1.76 eV at R = 1.3 Å. The true answer is E = −2.8 eV at R = 1.06 Å.
Why the poor agreement? Well, our ansatz must be seriously wrong in some
way; indeed, when R → 0, we just get the regular hydrogen ground state
wavefunction. But because the nuclear charge is 2e, the real ground state should
be the hydrogen ground state, contracted toward the origin by a factor of 2.
88
Tony Zhang
Part VI
Scattering
89
Tony Zhang 30 April 26, 2017 (recitation)
p2
H=
2m
(so V = 0). The eigenstates are
~
ψk ∝ eik·~x
with energies
h̄2 k 2
E=
.
2m
But our system is rotationally invariant, so we could alternatively use spherical
coordinates, giving eigenstates of the form
It will be very useful to be able to move between these two eigenbases. Thus,
we’d like to find expansion “coefficients” C such that
~
X
eik·~x = C~k,`,m (r)Y`m (Ω).
`,m
Without loss of generality, choose ~k = kẑ. Then we claim there’s a nice formula:
∞
ikz ikr cos θ
√ X √
e =e = 4π i` 2` + 1j` (kr)Y`,0 (Ω). (30.1)
`=0
h̄2
2
∂ u `(` + 1)
− 2 + u = Eu.
2m ∂r r2
h̄2 k2
Invoking E = 2m ,
∂ 2 u `(` + 1)
+− u = k 2 u.
∂r2 r2
This is the radial equation corresponding to the Helmholtz equation in spherical
coordinates, whose solutions u/r are superpositions of spherical Bessel func-
tions j` and n` , where n` is j` except with a cosine. Since n` blows up near 0,
we forbid its presence, so that
90
Tony Zhang 30 April 26, 2017 (recitation)
(Apparently there’s a cute way to get all solutions from the ` = 0 one by acting
with raising opeator p+ = px + ipy .)
Now we can express a Cartesian eigenstate as a superposition of the spherical
eigenstates of the same eigenvalue:
X
eikr cos θ = C`,m j` (kr)Y`m (Ω).
`,m
Acting with Lz , we see that the left hand side has eigenvalue 0; therefore the
Y`,m terms vanish unless m = 0, and we write C`,m = C` δm0 and
X
eikr cos θ = C` j` (kr)Y`0 (Ω). (30.3)
`
We claim that
n
L+
eikr cos θ = (−ikr)n sinn θeinφ eikr cos θ . (30.7)
h̄
2` `!
j` (ρ) → ρ` . (30.9)
(2` + 1)!
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Tony Zhang 30 April 26, 2017 (recitation)
and p
C` = i` 4π(2` + 1). (30.10)
Our desired result follows from plugging these coefficients back into the expansion
formula:
∞
√ X √
eikz = eikr cos θ = 4π i` 2` + 1j` (kr)Y`,0 (Ω). (30.11)
`=0
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Tony Zhang 31 April 27, 2017
p + p −−→ p + p + π0
p + p −−→ p + n + π+
e+ + e− −−→ μ+ + μ−
• Elastic scattering
• Spinless particles
• Non-relativistic scattering
• Interactions V (~r1 − ~r2 ) that we can turn into one-body problems by going
into the center-of-mass frame and using reduced masses.
• Energy eigenstates
h̄2 2
− ∇ + V (~r) ψ(~r) = Eψ(~r).
2M
For a scattering setup, we assume the potential has finite range a: that is, it
vanishes faster than r−1 for r → ∞. We look at scattering states: the solutions
of positive energy
h̄2 k 2
E= .
2M
So we want to solve
h̄2
∇2 + k 2 + V (~r) ψ(~r) = 0.
−
2M
The resulting solutions actually have infinite degeneracy— just consider the case
where V = 0.
Now in one-dimensional scattering, we would always posit an incident solution
Aeikx with reflection Be−ikx and transmission Ceikx . We’d like to do something
similar. Unfortunately, in 3D we don’t have a “left” and “right” side of the
potential.
Still, consider incident wave eikz . We can’t really talk about reflection and
transmission any more, so we just consider the scattered wave as one thing.
Naively, we ask whether a spherically symmetric outgoing wave eikr can be
considered a candidate scattered wave?
93
Tony Zhang 31 April 27, 2017
Actually, no, because it doesn’t solve the free-particle radial equation. But
we can divide by r to get a solution:
eikr
(∇2 + k 2 ) =0
r
which works for r 6= 0. But eikr /r doesn’t product angular dependence, which
is definitely something we want. So write
eikr
ψs (~x) = f (θ, φ)
r
with direction-dependent scattering amplitude f . Including fk makes this
solution only asymptotically: when r a. All together,
f (θ, φ)eikr
ψ(~r) = φ(~r) + ψs (~r) = eikz + .
r
We expect fk to be determined by the scattering potential.
Now we define the differential cross-section dσ as
particles scattered per unit time into solid angle dΩ
dσ = .
incident particle flux density
Intiutively, the cross-section gives an effective size of the scattering potential.
To compute cross-sections, let’s talk about probability currents. The denom-
inator is the incident probability current
h̄ h̄k
=(ψ ∗ ∇ψ) = ẑ
m m
where ψ = eikz . We can get this result also by intuitively observing that
probability current is just probability density multiplied by v:
p h̄k
|eikz |2 × = .
m m
Now scattered particles spend dt = drv time in volume element dr dΩ. So the
number of particles per unit time going through the volume element is
|f (Ω)|2 dr dΩ h̄k
dr
= |f (Ω)|2 dΩ
v
m
|f (Ω)|2 dΩ h̄k
dσ = h̄k
m
= |f (Ω)|2 dΩ.
m
As a result, we see that the scattering amplitude is a pretty good name for f .
Finally, we can define a total cross-section σ as the integral of all the dσ. Our
problem now is to look for scattering amplitude f (Ω).
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Tony Zhang 31 April 27, 2017
95
Tony Zhang 31 April 27, 2017
96
Tony Zhang 32 May 1, 2017 (recitation)
|fk (Ω)|2 2
Z Z
h̄k ~out
0= r dΩ + ~inter · dS
m r2
| {z }
σ
97
Tony Zhang 32 May 1, 2017 (recitation)
What is the flux contribution from ~inter ? Assuming large r, we have r̂ ≈ ẑ and
θ ≈ 0:
eik(r−z) e−ik(r−z)
Z Z
~ h̄k ∗ ~out
~inter · dSout = < fk (Ω) r̂ + fk (Ω) ẑ · dS
m r r
eik(r−z) e−ik(r−z)
Z
h̄k ∗
= < fk (θ = 0) + fk (0) dx dy
m r r
Because
r sin2 θ 1 1 x2 + y 2
r − z = r(1 − cos θ) = ≈ r sin2 θ =
1 + cos θ 2 2 r
we can continue
ik(x2 +y 2 )
Z Z !
~out 2h̄k e 2z
~inter · dS = < fk (0) dx dy
m z
Z ∞
2h̄k 2π ikρ2 /2z
= < fk (0) ρe dρ
m z 0
where we’ve gone into cylindrical coordinates and integrated away the azimuthal
ρ2
angle. Now substitute u = 2z to write
Z Z ∞
~out = 4πh̄k < fk (0)
~inter · dS eiku du
m 0
But the integral looks divergent. For a quick fix, we regulate it as:
Z ∞
1 i
ei(k+iε)u du = − =
0 i(k + iε) k + iε
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Tony Zhang 33 May 2, 2017
33 May 2, 2017
33.1 More about phase shifts
Recall our progress last time. We wanted a nice asymptotic form for the scattered
wavefunction for large r (far form the scattering center) in the case of a central
potential. We wrote
eikr
ψ(~r) ' eikz + f (θ) (33.1)
r
for r a, where a is the range of the spherically symmetric potential, which we
assume drops off faster than r−1 .
Now the free-particle Hamiltonian commutes with momentum and with angu-
lar momentum. But linear and angular momenta don’t commute! Diagonalizing
momentum with the Hamiltonian gives plane waves as eigenbasis; choosing
angular momentum gets us spherical waves.
We want to write ψ as a superposition of an ingoing spherical wave and an
outgoing one. The ingoing wave is fixed, since only the eikz term contributes to
ingoing probability current. That fixes the outgoing wave, by conservation of
probability, and we got a sum over ` of terms containing partial waves
`π `π
ei(kr− 2 +2δ` ) e−i(kr− 2 )
− . (33.2)
r r
In essence, we’re parameterizing our ignorance in two ways: either with f (which
is what we’re looking for) or with phase shifts δ` . It turns out that we can relate
the two by √ ∞
4π X √
f (θ) = 2` + 1Yl,0 (θ)eiδ` sin δ` . (33.3)
k
`=0
and
4π X
σ= (2` + 1) sin2 δ` . (33.5)
k2
`
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Tony Zhang 33 May 2, 2017
d2 u `(` + 1)
− u = −k 2 u. (33.9)
dr2 r2
If the potential vanishes outside some finite range a, the solution u/r for r > a
is
ψ(x)|` = (A` j` (kr) + B` n` (kr))Y`,0 (θ). (33.10)
Alternatively, if the potential decays sufficiently rapidly, ψ is a solution far away.
Basically, this ψ gives the form of a solution sufficiently far from the origin.
The B` term is a sign of scattering! Indeed, when there is no potential
(V = 0), this solution should hold all the way to the origin. But the spherical
Bessel functions n` are singular at r = 0. Therefore, their presence indicates
that there’s a potential making the solution near the origin something else that
eventually becomes ψ far out.
For kr large, we take the asymptotic expansions of the Bessel functions:
" #
sin(kr − `π
2 ) cos(kr − `π
2 )
ψ(x)|` ' A` − B` Y`,0 (θ). (33.11)
kr kr
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Tony Zhang 33 May 2, 2017
wave. Write
1 `π `π
ψ(x)|` ∝ sin kr − + tan δ` cos kr − Y`,0 (θ)
kr 2 2
1 `π `π
= cos δ` sin kr − + sin δ` cos kr − Y`,0 (θ)
kr cos δ` 2 2
1 `π
= sin kr − + δ` Y`,0 (θ) (33.13)
kr 2
so that
1 i(kr− `π +δ` ) `π
ψ(x)|` ∝ e 2 − e−i(kr− 2 +δ` ) Y`,0
2ikr
e−iδ` i(kr− `π +2δ` ) `π
= e 2 − e−i(kr− 2 )
2ikr
Our discussion shows that one can get the phase shift by any of three ways.
1. Use Equation 33.12 with the Bessel function solution outside the potential
range.
Because V vanishes for r > a, Equation 33.10 gives the exact radial solutions
u
= R` (r) = A` j` (kr) + B` n` (kr). (33.15)
r
A general solution is then a superposition
X
ψ(r, θ) = R` (r)P` (cos θ) (33.16)
`
where the P` are Legendre polynomials. But these are complete, so R` (a) = 0
for all `:
A` j` (ka) + B` n` (ka) = 0. (33.18)
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Tony Zhang 33 May 2, 2017
Then
B` j` (ka)
tan δ` = − = (33.19)
A` n` (ka)
which technically qualifies as having solved the problem, in that we understand
the Bessel functions well and that found the phase shifts.
Let’s find the scattering cross-section. The trig identity
tan2 δ`
sin2 δ` = . (33.20)
1 + tan2 δ`
gives
j`2 (ka)
sin2 δ` = (33.21)
j` (ka) + n2` (ka)
2
and thus
∞
4π X j`2
σ= (2` + 1) (ka). (33.22)
k2 j`2 + n2`
`=0
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Tony Zhang 33 May 2, 2017
A` j` (kr) + B` n` (kr).
The convenient way to solve this equation is to form the logarithmic derivative
aR`0 (a) A` je0 ll + B` n0`
0
j` − tan δ` n0`
β` (a) ≡ = ka = ka (33.30)
R` (a) A` j` + B` n` j` − tan δ` n`
At this point, we’re done in principle; it suffices to solve for tan δ` .
But sometimes people want to find e2iδ` . Unenlightening algebra gives
ka(j`0 − in0` ) − β` (j` − in` )
e2iδ` = − . (33.31)
ka(j`0 + in0` ) − β` (j` + in` )
hs
Writing Equation 33.27 as e2iδ` , it turns out that
j` −in`
hs β ` − ka( j` −in` )
e2iδ` = e2iδ` j 0 +in0
(33.32)
β` − ka( j`` −in`` )
(kr)2`+2
j` (kr)r2 , dr dΩ ∼ dr dΩ. (33.35)
(2` + 1)! !
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Tony Zhang 33 May 2, 2017
where we take the asymptotic form near the origin. (Far away from the origin,
j`2 r2 becomes a sine wave, as we have seen.) This asymptotic form is really tiny
until kr ≈ 1, at which point it takes off. The idea is that higher order partial
waves only become nontrivial somewhat far from the origin.
Remark 33.2 (Found in official class notes). In fact, considering scattering
scate with some k, the turning point can be found by equating energy with the
effective potential:
h̄2 `(` + 1) h̄2 k 2
= (33.36)
2mr2 2m
which gives a turning point r ≈ k` . We expect the solution j` (kr) to be
exponentially small within this turning point (i.e. in the classically foribdden
zone).
Recall
∞
4π X 2
X
σ= (2` + 1) sin δ ` ≡ σ` . (33.37)
k2
`=0 `
π π
σ' ((` + 1)2 − `2 ) = 2 (2` + 1). (33.40)
k2 k
The actual unitarity bound is larger by a factor of 4. Again, the mysterious
quantum scattering factor of 4; recall the hard sphere cross section.
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Tony Zhang 34 May 3, 2017 (recitation)
ψ(r, t = 0) = φ(r − r0 )
with impact parameter b, cross-sectional extent ∆r, and sharply defined wavevec-
tor k0 = k0 ẑ. We assume that r0 is sufficiently far from the origin such that
the entire wavepacket lies beyond the range a of the scattering potential. The
Fourier expansion of φ gives
Z
φ(r) = φ̃(k)eik·r d3 k.
eikr
ψk (r) = eik·r + fk (r̂) .
r
So for large r,
Z
ψ(r, t = 0) = φ̃(k)eik·(r−r0 ) d3 k
Z
' φ̃(k)ψk (r)e−ik·r0 d3 k
Z
φ̃(k) eik·r + ψks (r) e−ik·r0 d3 k.
=
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Tony Zhang 34 May 3, 2017 (recitation)
eikr
Z
ih̄k2 t
= φ̃(k) e ik·r
+ fk (r̂) e− 2m e−ik·r0 d3 k
r
≡ φ(r, t) + ψs (r, t) (34.1)
= φ(r − r0 − vt)eiω0 t
h̄k02
where ω0 = 2m . Our result makes sense, since the wave should travel at
h̄k0
velocity v = m . Now the scattered component looks like
106
Tony Zhang 35 May 4, 2017
35 May 4, 2017
35.1 Scattering integral equation
Begin with the time-independent Schrödinger equation:
h̄2 2 h̄2 k 2
− ∇ + V (r) ψ(r) = Eψ(r) = ψ(r). (35.1)
2M 2M
If we define U by
h̄2
V (r) = U (r). (35.2)
2M
Then we arrive at an inhomogeneous linear ordinary differential equation
Intuitively, G is the function that produces the δ-function response when acted
upon by the differential operator on the left hand side; having G allows us to
determine solutions for any response function by simple integration.
We claim that our differential equation is equivalent to
Z
ψ(r) = ψ0 (r) + G(r − r0 )U (r0 )ψ(r0 ) d3 r (35.5)
where ψ0 solves the homogeneous differential equation (∇2 + k 2 )ψ0 (r) = 0 (i.e.
it’s a free-particle plane wave). Let us check our particular solution:
Z
(∇ + k )ψ(r) = (∇2 + k 2 )G(r − r0 ) U (r0 )ψ(r0 ) d3 r0
2 2
| {z }
δ(r−r0 )
= U (r)ψ(r)
as desired.
Moving on. Recall that we earlier showed that
eikr
(∇2 + k 2 ) =0 (35.6)
r
for r 6= 0. Moreover, we know that
? 1 ±ikr
G± (r) = − e . (35.8)
4πr
Recall that G± must satisfy Equation 35.4.
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Tony Zhang 35 May 4, 2017
∇2 = ∇ · ∇
r
∇r =
r
∇ · (f v) = ∇f · v + f ∇ · v
r
∇f (r) = f 0 (r) .
r
Then we evaluate the Laplacian of G± :
2 2 ±ikr 1
∇ G± = ∇ e · −
4πr
2
1 1 1
= (∇2 e±ikr ) − + e±ikr ∇2 − + 2(∇e±ikr ) · ∇ −
4πr 4πr 4πr
∇2 G± = −k 2 G± + δ(r)
as desired. Therefore, we’ve found two good Green’s functions. Which one do
we take in the our integral equation (Equation 35.5)? Note the sign on the
exponent in each. We want to model scattering. To get an outgoing wave in
Equation 35.5, we pick
0
1 e+ik|r−r |
G+ (r − r0 ) = − . (35.9)
4π |r − r0 |
Now we can also choose ψ0 (r) = eikz to get our incident wave. Therefore, write
the integral equation as
Z
ψ(r) = e + G+ (r − r0 )U (r0 )ψ(r0 ) d3 r0 .
ikz
(35.10)
|r − r0 | = r − n · r0
and
1 ikr −ikn·r0
G+ (r − r0 ) ≈ − e e . (35.11)
4πr
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Tony Zhang 35 May 4, 2017
In general, we can write the incident wave as eikz 7→ eiki ·r . The outgoing
partial waves have ks ≡ nk. So we see that |ks | = |ki | = k. Then if the two k
are off by angle θ, their difference, the transfered momentum (well, wavenumber)
is
θ
K = |K| = 2k sin . (35.13)
2
where we’ve just taken Equation 35.10 and added primes. Then substituting
the second into the first, we can write
Z
0
ψ(r) = eiki ·r + G+ (r − r0 )U (r0 )eiki ·r d3 r0
Z Z
+ d r G+ (r − r )U (r ) d3 r00 G+ (r0 − r00 )U (r00 )ψ(r00 ).
3 0 0 0
We could go on, adding more and more terms by iterative substitution, in the
spirit of Picard iteration. In general, we can expand into a full series solution
ψ(r) = ψ (0) (r) + ψ (1) (r) + . . .
where ψ (0) (r) = eiki ·r and where
Z
ψ (k+1)
(r) = G+ (r − r0 )U (r0 )ψ (k) (r0 ) d3 r0 .
Usually we just take the first two terms to get the first Born approximation.
Then Equation 35.12 becomes
Z ikr
iki ·r 1 −iks ·r0 0 iki ·r0 3 0 e
ψ(r) = e + − e U (r )e d r (35.14)
4π r
| {z }
fk (θ,φ)
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Tony Zhang 35 May 4, 2017
can be interpreted as: taking the incident amplitude at each point in our
scattering potential, weighting by the potential, and propagating with G+ out to
our detector location r. (We’re convolving the amplitude contribution, weighted
by potential, with a term G+ that propagates things out to r.) The simple
picture is this contribution considers contributions from one wave deflection.
The second order term taking the contribution of the first order scattering,
weighting by potential, and propagating again, corresponding to two wave
deflections.
110
Tony Zhang 36 May 8, 2017 (recitation)
where we assume φ̃ has narrow support (that is, our initial wavepacket had very
small momentum uncertainty).
We now find
dNout ~out = v|f~ (Ω)|2 |φ(k̂0 r − ~r0 − ~v t)|2 dΩ
= ~out · dS k0 (36.10)
dt
so the cross-section numerator becomes
Z ∞
dNout dNout
= dt (36.11)
dΩ −∞ dt dΩ
Z ∞
= v|f~k0 (Ω)|2 |φ(k̂0 r − ~r0 − ~v t)|2 dt (36.12)
−∞
Z ∞
2
= |f~k0 (Ω)| |φ(−bx , −by , ξ)|2 dξ (36.13)
−∞
111
Tony Zhang 36 May 8, 2017 (recitation)
where we now recall that ~r0 = (bx , by , −|z0 |) and substitute ξ = r + |z0 | − vt.
Finally, we want to integrate over all possible impact parameters, since we
imagine a beam of particles of varying impact parameter, distributed as P (~b):
Z
dNout dNout ~
= d2~bP (~b) (b) (36.14)
dΩ dΩ
Z Z ∞
= d2~bP (~b)|f~k0 (Ω)|2 |φ(−bx , −by , ξ)|2 dξ (36.15)
−∞
Z
≈ P (0)|f~k0 (Ω)|2 |φ(−bx , −by , ξ)|2 dξ d2 b (36.16)
where we assume that the outgoing differential flux dNout /dΩ is sharply peaked
around ~b = 0.
Yay, a numerator. Now we consider the denominator of the cross-section.
Write
dNin h̄
= (=ψ ∗ ∇ψ) · ẑ (36.17)
dt dA m
h̄
= =(φ∗ (~r, t)∇φ(~r, t)) · ẑ. (36.18)
m
Now with
we get
dNin h̄k0
= |φ(~r − ~r0 − ~v t)|2 . (36.21)
dt dA m
Ingoing flux at (x, y, z) = (0, 0, −|z0 |), then, is
Z ∞
dNin dNin
(x = 0, y = 0, −|z0 |) = dt (36.22)
dA −∞ dt dA
Z ∞
=v |φ(−bx , −by , −vt)|2 dt (36.23)
−∞
Z ∞
= |φ(−bx , −by , ξ)|2 (36.24)
−∞
112
Tony Zhang 36 May 8, 2017 (recitation)
~ f (Ω) ikr
ψ(~r) = eiki ·~r + e . (36.30)
r
Write ~kf = kr̂. When is this approximation valid? Note that we have a series in
powers of U , so we want U to be small. But small compared to what?
Suppose the potential have depth V0 and spatial extent a. Then we want
the first term in the Born series small:
1 2m
a3 · · V0 1
a h̄2
or
h̄2
V0
, (36.32)
ma2
giving the regime where the Born approximation is valid: the potential is weak
and there is no bound state.
113
Tony Zhang
Part VII
Identical particles
114
Tony Zhang 37 May 9, 2017
37 May 9, 2017
37.1 Identical particles
In quantum mechanics, we say that two particles are identical if they have the
same intrinsic properties (mass, spin, charge, magnetic moment, etc.). Their
other properties may differ (e.g. momentum, angular momentum).
Example 37.1
If we have a particles at ~r0 and ~r00 with respective velocities ~v0 and ~v00 ,
Then we can write
Now suppose under the first labeling that we solve the system:
Since we claim the particles are identical, the Hamiltonian must be invariant
under particle exchange:
The two labeling choices are equivalent, so in classical mechanics, pick one
of them and stick to your choice!
115
Tony Zhang 37 May 9, 2017
where, since their wavepackets were all superimposed near the scattering
center.
2. A more serious issue: exchange degeneracy. To illustrate, we consider
two spin- 12 particles in states |+i , |−i. Now with composite systems, we
work in the tensor product Hilbert space. Then we have basis states
|vi i(1) ⊗ |vj i(2) . (We can also write |vi i ⊗ |vj i, or |vi i |vj i, or yet shorter,
|vi , vj i.)
So our spin- 12 system is in state |+i(1) ⊗ |−i(2) or |−i(1) ⊗ |+i(2) . Since the
particles are identical, physically, the two states are the same. Moreover,
scaling a state or taking linear combinations with identical states gives
the same state, so the state
is equivalent physically. (Note, however, that the two basis kets here are
actually orthogonal!)
What is the probability to find the particles in the state
(1) huk | ⊗ (2) hu` |P21 |ui i(1) ⊗ |uj i(2) = δkj δ`i
∗
† †
(1) huk | ⊗ (2) hu ` |P 21 |ui i(1) ⊗ |uj i(2) = (1) hui | ⊗ (2) hu j |P 21 |u k i (1) ⊗ |u` i(2)
= δ`i δkj
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Tony Zhang 37 May 9, 2017
Much like we can decompose all functions into odd and even functions, we
can decompose V ⊗ V = Sym2 V ⊕ Anti2 V . We introduce Hermitian projec-
tion operators S and A that (anti)symmetrize states (i.e. project onto the
(anti)symmetric subspace):
1
S= (1 + P21 ) (37.2)
2
1
A = (1 − P21 ) (37.3)
2
(From here, we refer only to Hermitian projection operators.) It is straight-
forward to verify that S 2 = S and A2 = A. Furthermore, S + A = 1, so the
projectors are complementary: they resolve the identity (albeit over a direct
sum decomposition instead of a basis).
Using the facts (easily checked) that P21 S = SP21 = S and P21 A = AP21 =
−A, it should be clear that S |ψi is symmetric and A |ψi is antisymmetric.
Before generalizing to more particles, we consider the action of S2 on opera-
tors. Let B ∈ Hom(V ) and define B(1) = B ⊗ 1 (and B(2) = 1 ⊗ B).
Then
†
P21 B(1)P21 |ui i(1) ⊗ |uj i(2) = P21 B(1) |uj i(1) ⊗ |ui i(2)
= P21 (B |uj i(1) ) ⊗ |u1 i(2)
= |ui i(1) ⊗ (B |uj i(2) )
= B(2) |ui i(1) ⊗ |uj i(2)
Here’s a sneak peak of the N -particle case: for each of the N ! permutations
σ ∈ SN , we have an operator Pσ (e.g. P231 ) that does an obvious thing:
P231 |ui i(1) ⊗ |uj i(2) ⊗ |uk i(3) = |uk i(1) ⊗ |ui i(2) ⊗ |uj i(3) .
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Tony Zhang 38 May 10, 2017 (recitation)
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Tony Zhang 39 May 11, 2017
Now recall how we define P231 last time. Expunge that from memory. We’re
now going to define
P231 |ui uj uk i = |uj uk ui i
where we use the shorthand |abc . . .i = |ai(1) ⊗ |bi(2) ⊗ . . . .
What is the inverse of P231 ? Why, it’s simply P312 , corresponding to the
inverse of the original permutation in S3 .
In general, we can consider general permutation operators Pα where α ∈ SN
is a permutation of {1, . . . , N }. We can think of it as a list {α(1), . . . , α(N )}.
They act as
Pα |u1 u2 . . . uN i = |uα(1) uα(2) . . . uα(N ) i . (39.1)
Example 39.1
P3142 |u1 u2 u3 u4 i = |u3 u1 u4 u2 i .
Example 39.2
Heavily abbreviating,
Note that this composition is the reverse of what you might expect from
group theory. Indeed, we’re using the law of composition στ = τ ◦ σ: we’re
using right multiplication.
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Tony Zhang 39 May 11, 2017
Now recall that P21 is Hermitian (by inner-product-bash) and unitary (be-
2
cause P12 = 1). By the same argument, Pt is unitary for any transposition t.
Since transpositions generate SN , any Pα is unitary. However, they’re not all
†
Hermitian! (For example, consider P312 .)
Joke. (On the group multiplication table for S3 ) “It’s like sudoku!” –zwiebach
Pα S = SPα = S (39.4)
Pα A = APα = α A (39.5)
S2 = S A2 = A SA = AS. (39.6)
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Tony Zhang 39 May 11, 2017
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Tony Zhang 40 May 15, 2017 (recitation)
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Tony Zhang 40 May 15, 2017 (recitation)
Example 40.1
Consider two identical spin- 12 particles. So our Hilbert space is V ⊗ V ,
where V ∼= C2 . Acting on the product space basis with S gives three
symmetric states
S |↑↑i = |↑↑i
|↑↓i + |↑↓i
S |↑↓i = S |↓↑i =
2
S |↓↓i = |↓↓i
A |↑↑i = 0
|↑↓i − |↓↑i
A |↑↓i =
2
|↓↑i − |↑↓i
A |↓↑i =
2
A |↓↓i = 0
If we have fermions, we see that we cannot have both particles in the same
spin state. This is basically the Pauli exclusion principle.
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Tony Zhang 41 May 16, 2017
Some comments:
Then
!
X X X
|ψi = S |ψi = cα SPα |ui = cα S |ui = S |ui cα
α α α
which is parallel to S |ui, which we now see gives the unique symmetric
subspace of V|ui .
Antisymmetrization is a little more involved.
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Tony Zhang 41 May 16, 2017
It’s important that we keep the labels on the kets: we might get a term like
− |ϕi(2) ⊗ |χi(1) ⊗ |ωi(3) , which is really the state − |χϕωi.
It’s nice how the signs work out with the determinant. In fact, the definition
of A |ui matches that of the determinant
X N
Y
det B = α Bα(i),i , (41.1)
α i=1
whence
1 X 1 X O 1
A |ωi = α Pα |ωi = α ωα(i),i = det ωij .
N! α N! α i
N !
This determinant is called the Slater determinant. It’s clear that we can’t
have two |ωi i the same, because then the determinant vanishes. So two fermions
cannot occupy the same state: this is the Pauli exclusion principle!
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Tony Zhang 41 May 16, 2017
P
The tensor product is finite, since k nk = N . These states are all orthogonal
too!
We summarize our discussion with the following:
Proposition 41.1
• For N bosons, the states in SymN V are |n1 n2 . . .i with nonnegative
integer occupation numbers ni summing to N .
In general, defining
we can write
1 1
|γabi = (|γabi + |γbai) + (|γabi − |γbai) (41.5)
2 2
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Tony Zhang 43 May 17, 2017 (recitation)
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Tony Zhang 44 May 18, 2017
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Tony Zhang 44 May 18, 2017
For identical particles, specifying the occupation numbers Ni gives the state
uniquely. So it remains to consider the number of ways we can arrange particles
within the degenerate subspaces. For subspace i, there are
di di !
= (44.7)
Ni Ni ! (di − Ni )!
so that
Y di + Ni − 1
QBE = . (44.10)
i
Ni
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Tony Zhang 44 May 18, 2017
tells us that all states with equal total energy are equally likely when we’re in
thermal equilibrium.
P
P Therefore, we maximize Q subject to constraints N = i Ni and E =
i N i Ei . It’s actually more convenient to maximize log-likelihood ln Q, which
we’ll do with Lagrange multipliers. Define Lagrangian
! !
X X
f (N1 , . . . ; α, β) = ln Q(N1 , . . . ) + α N − Ni + β E − Ei Ni .
i i
(44.11)
We’ll be considering factorials with large arguments, so we use Stirling’s
approximation
√ n n
n! ∼ 2πn , (44.12)
e
or, taking logs,
ln n! ∼ n ln n − n. (44.13)
Then the log-likelihood in the Fermi-Dirac case is
X di !
ln QFD = ln
i
Ni ! (di − Ni )!
X
= (ln di ! − ln Ni ! − ln(di − Ni )! )
i
X
≈ di ln di − Ni ln Ni − (di − Ni ) ln(di − Ni )
i
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Tony Zhang A Useful formulae
A Useful formulae
A.1 Wave mechanics
Probability current
h̄
~ = =(ψ ∗ ∇ψ) (A.1)
m
A.2 Spin- 12
These obey
λ = a0 ± |~a|. (A.4)
√
r
2h̄
x0 = p0 = 2h̄mω, (A.6)
mω
creation and annihilation operators
x̂ p̂ x̂ p̂
â = +i â† = −i (A.7)
x0 p0 x0 p0
and number operator
N̂ = â† â. (A.8)
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Tony Zhang A Useful formulae
J± = Jx ± iJy . (A.12)
Also,
4πε0 = 1. (A.16)
B
and magnetic fields should be converted from SI as B 7→ c.
p̂2 e2 h̄2 2 e2
Ĥ = − =− ∇ − . (A.17)
2me r̂ 2me r
Bohr radius:
h̄2 h̄
a0 = = = 52.918 pm. (A.18)
me e2 αmc
Energy levels:
e2 1 α2 mc2 13.6 eV
En = − = − =− . (A.19)
2a0 n2 2 n2 n2
Simultaneous Ĥ, L̂2 , L̂z eigenstates:
s 3
2 (n − ` − 1)! − 1 ρ ` 2`+1
ψn`m (r, θ, φ) = e 2 ρ Ln−`−1 (ρ)Y`m (θ, φ) (A.20)
na0 2n(n + `)!
where L2`+1
n−`−1 is a generalized Laguerre polynomial of degree n − ` − 1, and
where Y`m is a spherical harmonic (orthonormalized, with the Condon-Shortley
phase convention).
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Tony Zhang A Useful formulae
Ground state:
1 r
ψ100 (r, θ, φ) = p 3 e− a0 (A.22)
πa0
n = 2 states:
1 r r
ψ200 = p 1 − e− 2a0 (A.23)
8πa03 2a0
1 ∓x − iy − 2ar
ψ21,±1 = p 3 e 0 (A.24)
8 πa0 a0
1 z − 2ar
ψ210 = p e 0 (A.25)
4 2πa0 a0
3
p2 p4 1 1 dV h̄2
H= +V − 3 2
+ 2 2
S · L + 2 2
∇2 V (A.27)
|2m{z } |8m{zc } |2m c r{zdr } |8m c{z }
H0 δHrel δHspin-orbit δHDarwin
1 α4 mc2
(1) n 3
δEn,j = − 1 − (A.28)
2 n4 j+ 2
4
(H 0 −En(0) ) |n(k) i = (En(1) −δH) |n(k−1) i+En(2) |n(k−2) i+· · ·+En(k) |n(0) i (A.32)
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Tony Zhang A Useful formulae
and resolve the identity as necessary. Most useful is the first order wavefunction
shift:
X δHkn
|n(1) i = − (0) (0)
|k (0) i (A.33)
E
k6=n k − En
For valid first order results, we must choose a “good basis” in which we diago-
nalize δH in degenerate subspace n:
(1)
(δH)nl,nk = Enk δlk . (A.35)
A sufficient condition for the goodness of a basis is the existence of a complete
set of commuting observables on our degenerate subspace with our basis as
common eigenbasis that also commutes with δH.
(1)
If all the Enk are different, degeneracy is broken to first order, and the
first-order wavefunction shifts are
X δHp,nk XX δHnl,p δHp,nk
|n(1) ; ki = (0) (0)
+ (0) (0) (1) (1)
|n(0) ; li
p6=n En − Ep l6=k p6=n (En − Ep )(Enk − Enl )
(A.36)
The second order energy shifts will come easily.
Otherwise, our “good basis” is only good to first order. To get second order
energy shifts and first order wavefunction shifts, we’ll need to go to second order.
A basis good to second order must diagonalize
(2)
X δHnl,p δHp,nk
Mlk = (0) (0)
. (A.37)
p6=n En − Ep
(2)
The resulting eigenvalues are the En .
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Tony Zhang A Useful formulae
and
∂
|ψ̃(t)i = δH(t)
ih̄ f |ψ̃(t)i . (A.46)
∂t
The perturbative solution, to second order, is just
t0
!
Z t Z t Z
1 0 f 0) + 1 0 00 0 f 00
|ψ̃(t)i = 1+ dt δH(t dt dt δH(t )δH(t ) |ψ̃(0)i
f
ih̄ 0 (ih̄)2 0 0
(A.47)
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Tony Zhang A Useful formulae
where d~ is the dipole moment operator. These coefficients give the rates of
spontaneous emission and of stimulated emission per unit spectral energy density,
respectively, for an atom subject to thermal radiation, with spectral energy
density given by Equation A.52.
The actual absorption rate is Bab U (ωab )Na ; stimulated emission, Bab U (ωab )Nb ;
spontaneous emission, ANb . Use the fact that Na ∝ e−βEa .
`0 − ` = ±1 m0 − m = −1, 0, 1. (A.50)
A.9 Thermodynamics
Thermodynamic beta:
1
β= . (A.51)
kT
Spectral energy density of blackbody radiation,
ω3
h̄
U (ω) = 2 3 . (A.52)
π c eβh̄ω − 1
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Tony Zhang A Useful formulae
1 t
Z Z t
θn (t) = − En (t0 ) dt0 γn (t) = i hψn (t0 )|ψ̇n (t0 )i dt0 . (A.55)
h̄ 0 0
|H12 |2
= ωτ 1. (A.56)
h̄|α|
The probability of diabatic passage is
|H12 |2
P = exp −2π . (A.57)
h̄α
Assume R ~ changes adiabatically, so we can assume it’s fixed. Then solve for
electron wavefunctions
~ R (R).
(Ke + VN e + Vee )φR (~r) = Ee (R)φ ~ (A.61)
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Tony Zhang A Useful formulae
with
X h̄2 Z 2
X A2
α
U (R) = VN N (R) + Ee (R) + |∇R φR (r)| dr − (A.64)
α
2M α α
2M α
~ ~r)|H|ψ(R,
satisfying hψ(R, ~ ~r)i = hη(R)|H
~ eff |η(~
r)i.
A.11 Scattering
A.11.1 Partial waves and phase shifts
Given poential with finite range a, we would like to write energy eigenstates as
eikr
ψ(r) = ψincident (r) + ψscattered (r) ' eikz + fk (θ, φ) (A.65)
r
h̄2 k2
where the last part holds for r a. We have energy E = 2m and differential
cross-section
dσ
= |fk (θ, φ)|2 . (A.66)
dΩ
Optical theorem
4π
σ= =fk (θ = 0). (A.67)
k
Plane waves can be expanded in terms of spherical partial waves
∞
√ X √
eikz = eikr cos θ = 4π i` 2` + 1j` (kr)Y`,0 (θ) (A.68)
`=0
A consequence is that
4π X
σ= (2` + 1) sin2 δ` . (A.71)
k2
`
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Tony Zhang A Useful formulae
Also, using L ' h̄` ' bp = h̄bk for impact parameter b, we get b = `/k.
There shouldn’t be scattering for k` > a.
TODO TODO TODO insert hard sphere scattering
Green’s function
1 eikr
G+ (r) = − (A.76)
4π r
satisfies defining relation
Born series
Z
0
ψ(r) = eiki ·r + G+ (r − r0 )U (r0 )eiki ·r d3 r0
Z Z
+ d r G+ (r − r )U (r ) d3 r00 G+ (r0 − r00 )U (r00 )ψ(r00 ). (A.79)
3 0 0 0
To first order,
eikr
ψ(r) = eiki ·r + fk (θ, φ) (A.80)
r
where the scattering amplitude is just
Z
1 0
fk (θ, φ) = − e−iK·r U (r0 ) d3 r0 . (A.81)
4π
For radial potentials V :
Z ∞
2m
fk (θ) = − rV (r) sin(Kr) dr (A.82)
Kh̄2 0
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Tony Zhang A Useful formulae
These form a representation of symmetric group SN . All Pα are unitary, but not
all are Hermitian. One class of α give Hermitian operators: the transpositions.
Symmetrizer and antisymmetrizer
1 X 1 X
S= Pα A= ε α Pα (A.84)
N! α N! α
project onto SymN V and AntiN V , which are the state spaces of N -particle
ensembles of bosons and fermions, respectively.
O 1
A |ωi i(i) = det |ωi i(j) . (A.85)
i
N!
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Tony Zhang B Useful math
B Useful math
B.1 Trigonometric integrals
Average of sin2 and cos2 over a sphere.
Z Z
1 1 1 2
cos2 θ dΩ = sin2 θ dΩ = . (B.1)
4π 3 4π 3
To remember: sin2 θ is larger over the equatorial region, which is larger on the
sphere than the polar regions where cos2 θ is large.
1
Y00 (θ, φ) = √ (B.10)
4π
r
3
Y10 (θ, φ) = cos θ (B.11)
4π
r
3
Y1,±1 (θ, φ) = ∓ sin θe±iφ (B.12)
8π
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Tony Zhang B Useful math
For degrees n ≤ 2:
Lα
0 (x) = 1 (B.14)
Lα
1 (x) = −x + α + 1 (B.15)
1 2
Lα
2 (x) = x − 2(α + 2)x + (α + 1)(α + 2) (B.16)
2
where ρ = kr.
They can be defined as
` `
1 ∂ sin ρ 1 ∂ cos ρ
j` (ρ) = (−ρ)` n` (ρ) = −(−ρ)` . (B.18)
ρ ∂ρ ρ ρ ∂ρ ρ
To get from j` to n` , replace cos ρ 7→ sin ρ and sin ρ 7→ − cos ρ. The first two j`
and n` are
sin ρ
j0 (ρ) = (B.19)
ρ
sin ρ cos ρ
j1 (ρ) = 2 − (B.20)
ρ ρ
cos ρ
n0 (ρ) = − (B.21)
ρ
cos ρ sin ρ
n1 (ρ) = − 2 − (B.22)
ρ ρ
The n` are singular at the origin.
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