5.

61 Fall 2007 Lecture #21 page 1

HYDROGEN ATOM
Schrodinger equation in 3D spherical polar coordinates:

!2 ⎡ 1 ∂ ⎛ 2 ∂ ⎞ 1 ∂ ⎛ ∂⎞ 1 ∂2 ⎤
− ⎢ r +
2 µ ⎣ r 2 ∂r ⎜⎝ ∂r ⎟⎠ r 2 sin θ ∂θ ⎜⎝
sin θ + ( ) (
⎥ ψ r,θ ,φ + U r,θ ,φ ψ r,θ ,φ = Eψ r,θ ,φ
∂θ ⎟⎠ r 2 sin 2 θ ∂φ 2 ⎦
) ( ) ( )

−Ze2
with Coulomb potential U (r) =
4πε 0 r
Rewrite as

⎡ 2 ∂⎛ 2 ∂⎞ ⎤
⎢ −! ⎜ r ⎟
∂r ⎝ ∂r ⎠
()
+ 2 µr 2 ⎡⎣U r − E ⎤⎦ ⎥ ψ r,θ ,φ + L̂2ψ r,θ ,φ = 0 ( ) ( )
⎣ ⎦

function of r only function of θ,φ only

ˆH ⇒
r is separable ψ is separable

Y
ml
Angular momentum: solutions are spherical harmonic wavefunctions

( )
ψ r,θ ,φ = R r Yl m θ ,φ () ( )
with L̂2Yl m (θ ,φ ) = ! l ( l + 1)Y (θ ,φ )
2
l
m
l = 0,1,2,...

Radial equation for the H atom:

!2 d ⎛ 2 dR r ⎞ ⎡ ! l l + 1
2
() ⎤ ( )
− ⎜
2 µr 2 dr ⎝
r ⎟ + ⎢
dr ⎠ ⎢⎣ 2 µr 2
+ U r − E ⎥R r = 0 () ()
⎥⎦

()
Solutions R r are the H atom radial wavefunctions

Simplest case: l = 0 yields solution

32
⎛Z⎞
()
R r = 2⎜ ⎟
⎝ a0 ⎠
e
− Zr a0
exponential decay away from nucleus
5.61 Fall 2007 Lecture #21 page 2

with

E = − Z 2 e2 8πε 0 a0 lowest energy eigenvalue

a0 ≡ ε 0 h2 πµe2 Bohr radius

General case: solutions are products of (exponential) x (polynomial)

Energy eigenvalues:

−Z 2 e2 −Z 2 µe4
E= = n = 1,2,3,...
8πε 0 a0 n2 8ε 02 h2 n2

Radial eigenfunctions:

12
⎡ ⎤
( )
n − l − 1 ! ⎥ ⎛ 2Z ⎞
l +3 2
⎛
− Z r na0 2l +1 2 Zr
⎞
Rnl ()
r =− ⎢
⎢ ⎜
⎥ ⎝ na ⎠⎟ r le Ln+ l ⎜ ⎟
( )
3
2n ⎡ n + l !⎤ ⎝ na0 ⎠
⎣⎢ ⎣ ⎦ ⎦⎥
0

( )
where L2ln++1l 2Zr na0 are the associated Laguerre functions, the first few of which are:
n=1 l=0 L11 = −1
⎛ ⎞
n=2 l=0 L12 = −2!⎜ 2 − Zr ⎟
⎝ a0 ⎠
l =1 L33 = −3!
⎛ 2 2 ⎞
n=3 l=0 L13 = −3!⎜ 3 − 2Zr + 2Z r 2⎟
⎝ a0 9a0 ⎠
⎛ ⎞
l =1 L34 = −4!⎜ 4 − 2Zr
⎝ 3a0 ⎟⎠
l=2 L55 = −5!

Normalization:
( ) ( )
2π π
Spherical harmonics ∫ 0
dφ ∫ dθ sin θ Yl m* θ ,φ Yl m θ ,φ = 1
0

() ()
∞
Radial wavefunctions ∫ 0
dr r 2 Rnl* r Rnl r = 1
5.61 Fall 2007 Lecture #21 page 3

TOTAL HYDROGEN ATOM WAVEFUNCTIONS

( ) () ( )
ψ nlm r,θ ,φ = Rnl r Yl m θ ,φ

principle quantum number n = 1,2,3,...

angular momentum quantum number l = 0,1,2,..., n − 1
magnetic quantum number m = 0, ±1, ±2,..., ±l

ENERGY depends on n: E = −Z 2 e2 8πε 0 a0 n2

ORBITAL ANGULAR MOMENTUM depends on l: (

L = ! l l +1 )
ANGULAR MOMENTUM Z-COMPONENT depends on m: Lz = m!

Total H atom wavefunctions are normalized and orthogonal:

( ) ( )
2π π ∞
∫ dφ ∫ sin θ dθ ∫ r 2 dr ψ nlm r,θ ,φ ψ n ' l ' m ' r,θ ,φ = δ nn 'δ ll 'δ mm '
*
0 0 0

() ( )
since components Rnl r Yl m θ ,φ are normalized and orthogonal.

Lowest few total H atom wavefunctions, for n = 1 and 2 (with σ = Zr a0 ):

5.61 Fall 2007 Lecture #21 page 4

3/ 2
1 ⎛Z⎞
n=1 l=0 m=0 ψ 100 = ⎜ ⎟ e− σ = ψ 1s
π ⎝ a0 ⎠
3/ 2
1 ⎛Z⎞
n=2 l=0 m=0 ψ 200 = ⎜ ⎟ (2 − σ ) e −σ / 2
= ψ 2s
32π ⎝ a0 ⎠
3/ 2
⎛Z⎞
1
l =1 m=0 ψ 210 = ⎜ ⎟ σ e− σ / 2 cosθ = ψ 2 p
32π ⎝ a0 ⎠ z

3/ 2
⎛Z⎞ 1
l =1 m = ±1 ψ 21±1 = ⎜ ⎟ σ e− σ / 2 sin θ e± iφ
64π ⎝ a0 ⎠
or the alternate linear combinations
3/ 2
⎛Z⎞
1 1
ψ2p = ⎜ ⎟ σ e− σ / 2 sin θ cos φ = (ψ 21+1
+ ψ 21−1 )
x
32π ⎝ a0 ⎠ 2
3/ 2
⎛Z⎞
1 1
ψ2p = ⎜ ⎟ σ e− σ / 2 sin θ sin φ = (ψ 21+1
− ψ 21−1 )
y
32π ⎝ a0 ⎠ 2i

The value of l is denoted by a letter: l = 0,1,2,3...

s,p,d,f orbitals

The value of m is denoted by a letter for l = 1: m = 0, ± 1 linear combinations

pz , px ,p y orbitals
HYDROGEN ATOM ENERGIES

Potential energy of two electrons separated by the Bohr radius:

U = e2 4πε 0 a0 _ one “atomic unit” (a.u.) of energy.

H atom energies: E = −Z 2 e2 8πε 0 a0 n2 = −Z 2 2 n2 a.u.

n En (a.u.)
1 -1/2
2 -1/8
3 -1/18
4 -1/32
5 -1/50
! !
∞
0
5.61 Fall 2007 Lecture #21 page 5

H atom energies &transitions E E/hc

n (a.u.) (cm-1)
0 0
4 -1/32 -6,855
3 -1/18-12,187

2 -1/8

1 -1/2 -109,680

H atom emission spectra

Lyman series Balmer Paschen

λ(A)

ν(1012 Hz)

DEGENERACIES OF H ATOM ENERGY LEVELS

As n increases, the degeneracy of the level increases.

What is the degeneracy gn of each level as a function of n?
Does this help understand the periodic table?
5.61 Fall 2007 Lecture #21 page 6

SHAPES AND SYMMETRIES OF THE ORBITALS

S ORBITALS
( ) ( )( )
−1 2 −r / a0 −r / 2a0
ψ 1s = π a03 e ψ 2s = 32π a03 2 − r a0 e
l=0 spherically symmetric
n - l -1 = 0 radial nodes n - l -1 = 1
l=0 angular nodes l=0
n -1 = 0 total nodes n -1 = 1

( )
2
Electron probability density given by ψ r,θ ,φ
Probability that a 1s electron lies between r and r + dr of the nucleus:

( ) ( ) ( )
2π π −1 −2r / a0 2
∫
0
dφ ∫ dθ sin θ ψ 1s* r,θ ,φ ψ 1s r,θ ,φ r 2 dr = 4π π a03
0
e r dr

1l=
P ORBITALS: wavefunctions

Not spherically symmetric: depend on θ ,φ

( ) (r a ) e
−1/ 2 −r / 2a0
m = 0 case: ψ 210 = ψ 2 p = 32π a03 0
cosθ
z

⇒
ψ 2 p independent of φ symmetric about z axis
z

radial nodes n - l -1 = 0 ()
(note difference from 2s: Rnl r depends on l as well as n)
angular nodes l =1
total nodes n -1 = 1

xy nodal plane – zero amplitude at nucleus

( ) (r a ) e
−1/ 2 −r / 2a0
ψ 2 p = 32π a03 0
sin θ cos φ
m = ±1 case: Linear combinations give
x

= ( 32π a ) ( r a ) e
−1/ 2 −r / 2a0
ψ2p 3
0 0
sin θ sin φ
y

Equivalent probability distributions

5.61 Fall 2007 Lecture #21 page 7

H atom radial probability densities

0.6

0.5

()
0.4

r 2 Rnl2 r a0
() 220nlrRra
0.3
0.6 0.6

0.2
0.5 0.5

0.1
2s
0.4 0.4

1s 0.6
0
0 5 10 15 20 25 30
0.3 0.3

0.5
0.2 0.2

0.1
0.4
0.1
2p
0.6
0.3
0 0
0 5 10 15 20
0 25
5 10
30 15 20 25 30
0.5
0.2

0.4
0.1
0.6
3s
0.3
0
0.5 0 5 10 15 20 25 30
0.2

0.4
0.1
3p
0.3
0
0 5 10 15 20 25 30
0.2

3d
0.1

0
0 5 10 15 20 25 30

s = r/a0
5.61 Fall 2007 Lecture #21 page 8

MAGNETIC FIELD EFFECTS

Electron orbital angular momentum (circulating charge) magnetic moment

μ=− e
L
2me

Magnetic field B applied along z axis interacts with μ:

Potential energy

U = −μ•Β = −μ zΒz = eBz Lz

2me

Include in potential part of Hamiltonian operator:

eBz
Ĥ = Ĥ 0 + L̂
2me z

H atom wavefunctions are eigenfunctions of both Ĥ 0 and L̂z operators

eigenfunctions of new Ĥ operator.

Energy eigenvalues are the sums

Z 2 e2 eB
E= 2
+ z m
8 0 a0 n 2me

Energy depends on magnetic quantum number m when a magnetic field is applied.

2p orbitals: m = -1,0,+1 states have different energies

Splitting proportional to applied field Bz.
5.61 Fall 2007 Lecture #21 page 9

Applied
magnetic field
No magnetic
m = +1
field
2p m=0
m = -1

Energy

1s m=0
2p →
1s Emission spectra
One line Three lines

Complex functions ψ 21−1 and ψ 21+1 are eigenfunctions of L̂z with eigenvalues ±m! .

ψ 2 p and ψ 2 p are eigenfunctions of Ĥ 0 but not of L̂z ⇒ no longer energy

x y

eigenfunctions once magnetic field is applied.

5.61 Physical Chemistry 23-Electron Spin page 1

ELECTRON SPIN

Experimental evidence for electron spin

Compton Scattering (1921): AH Compton suggested that “the electron is

probably the ultimate magnetic particle.”

Stern­Gerlach Experiment (1922): Passed a beam of silver atoms (4d105s1)

through an inhomogeneous magnetic field and observed that they split into two
beams of space quantized components.

Uhlenbeck and Goudsmit (1925) showed that these were two angular
momentum states – the electron has intrinsic angular momentum – "SPIN"
angular momentum

Pauli Exclusion Principle (1925): no more than 2 electrons per orbital, or,
no two electrons with all the same quantum numbers. Additional quantum
number, now called ms, was postulated.

Postulate 6: All electronic wavefunctions must be

antisymmetric under the exchange of any two electrons.

Theoretical Justification
Dirac (1928) developed relativistic quantum theory & derived electron
spin angular momentum

Orbital Angular Momentum

L = orbital angular momentum
L = � l (l + 1 )
l = orbital angular momentum quantum number
l ≤ n −1
Lz = m �
m = 0, ±1, ±2, …, ±l
5.61 Physical Chemistry 23-Electron Spin page 2

Spin Angular Momentum

S ≡ spin angular momentum
S = � s (s + 1 ) = � 3 2
s = spin angular momentum quantum number
s =1 2
Sz = ms �
ms = ± 1 2
Define spin angular momentum operators analogous to orbital angular momentum
operators

L2Yl m (θ , φ ) = l ( l + 1) � 2Yl m (θ , φ ) l = 0,1, 2,...n for H atom

LzYl m (θ , φ ) = m�Yl m (θ , φ ) m = 0, ±1, ±2,... ± n for H atom

1
Ŝ 2α = s ( s + 1) � 2α Ŝ 2 β = s ( s + 1) � 2 β s= always
2
1 1
Ŝ zα = ms �α mαs = Ŝ z β = ms �β msβ = −
2 2

Spin eigenfunctions α and β are not functions of spatial coordinates so the

equations are somewhat simpler!

α ≡ "spin up" β ≡ "spin down"

Spin eigenfunctions are orthonormal:

∫ α α dσ = ∫ β β d σ = 1
* *
σ ≡ spin variable

∫ α β dσ = ∫ β α d σ = 0
* *

Spin variable has no classical analog. Nevertheless, the angular momentum of

the electron spin leads to a magnetic moment, similar to orbital angular
momentum.
5.61 Physical Chemistry 23-Electron Spin page 3

Electron orbital magnetic moment Electron spin magnetic moment

e e
µL = − L µs = − gS
2me 2me
e� e�
µL = − l ( l + 1) ≡ − β 0 l ( l + 1) µs = − g s ( s + 1) = − β 0 g s ( s + 1)
2me 2me
e e� e e�
µLz = − Lz = − m = − β 0m µSz = − gS z = − gms = − β 0 gms ≈ ± β 0
2me 2me 2me 2me
g ≡ "electronic g factor" = 2.002322

Total electronic wavefunction has both SPATIAL and SPIN parts.

Each part is normalized so the total wavefunction is normalized

Ψ ( r, θ , φ , σ ) = ψ ( r, θ , φ ) α (σ ) or ψ ( r, θ , φ ) β (σ )

e.g. for H atom the ground state total wavefunctions (in atomic units) are

12 12
⎛ Z3 ⎞ ⎛ Z3 ⎞
Ψ 1 = ⎜ ⎟ e − Zrα Ψ 1 = ⎜ ⎟ e − Zr β
100
2 ⎝π ⎠ 100−
2 ⎝π ⎠

which are orthogonal and normalized. Note the quantum numbers are now ­­
nlmmS
5.61 Physical Chemistry 24 Pauli Spin Matrices Page 1

Pauli Spin Matrices

It is a bit awkward to picture the wavefunctions for electron spin because –
the electron isn’t spinning in normal 3D space, but in some internal dimension
that is “rolled up” inside the electron. We have invented abstract states “α”
and “β” that represent the two possible orientations of the electron spin,
but because there isn’t a classical analog for spin we can’t draw “α” and “β”
wavefunctions. This situation comes up frequently in chemistry. We will
often deal with molecules that are large and involve many atoms, each of
which has a nucleus and many electrons … and it will simply be impossible for
us to picture the wavefunction describing all the particles at once.
Visualizing one­particle has been hard enough! In these situations, it is most
useful to have an abstract way of manipulating operators and wavefunctions
without looking explicitly at what the wavefunction or operator looks like in
real space. The wonderful tool that we use to do this is called Matrix
Mechanics (as opposed to the wave mechanics we have been using so far).
We will use the simple example of spin to illustrate how matrix mechanics
works.

The basic idea is that we can write any electron spin state as a linear
combination of the two states α and β:
ψ ≡ cαα + cβ β
Note that, for now, we are ignoring the spatial part of the electron
wavefunction (e.g. the angular and radial parts of ψ). You might ask how we
can be sure that every state can be written in this fashion. To assure
yourself that this is true, note that for this state, the probability of finding
2 2
the electron with spin “up” (“down”) is cα ( cβ ). If there was a state that
could not be written in this fashion, there would have to be some other spin
state, γ, so that
ψ ≡ cαα + cβ β + cγ γ
2
In this case, however, there would be a probability cγ of observing the
electron with spin γ – which we know experimentally is impossible, as the
electron only has two observable spin states.

The basic idea of matrix mechanics is then to replace the wavefunction

with a vector:
 1

5.61 Physical Chemistry 24 Pauli Spin Matrices Page 2

⎛ cα ⎞
ψ ≡ cαα + cβ β
ψ≡⎜ ⎟ →
⎝ cβ ⎠
Note that this is not a vector in physical (x,y,z) space but just a convenient
way to arrange the coefficients that define ψ. In particular, this is a nice
way to put a wavefunction into a computer, as computers are very adept at
dealing with vectors.

Now, our goal is to translate everything that we might want to do with the
wavefunction ψ into something we can do to the vector ψ . By going through
this step­by­step, we arrive at a few rules

Integrals are replaced with dot products. We note that the overlap
between any two wavefunctions can be written as a modified dot product
between the vectors. For example, if φ ≡ dαα + d β β then:

1 0 0 1

∫ φ ψ dσ = dα cα ∫ α α dσ + dα cβ ∫ α β dσ + dβ cα ∫ β α dσ + dβ cβ ∫ β β dσ
* * * * * * * * *

= dα *cα + d β *cβ
⎛ cα ⎞
(
= dα * )
dβ * ⎜ ⎟
⎝ cβ ⎠
≡ φ† iψ
ψ
Where, on the last line, we defined the adjoint of a vector:
†
⎛ x1 ⎞ * *
⎜ x ⎟ ≡ x1 x2 .
⎝ 2⎠
( )
Thus, complex conjugation of the wavefunction is replaced by taking the
adjoint of a vector. Note that we must take the transpose of the vector
and not just its complex conjugate. Otherwise when we took the overlap we
would have (column) x (column) and the number of rows and columns would
not match.

These rules lead us to natural definitions of normalization and orthogonality

of the wavefunctions in terms of the vectors:
⎛ cα ⎞ 2
∫ ( 2
ψ *ψ dσ = 1 → ψ†iψ = cα * cβ * ⎜ ⎟ = cα + cβ = 1 )
⎝ cβ ⎠
and
5.61 Physical Chemistry 24 Pauli Spin Matrices Page 3

⎛ cα ⎞
∫ φ ψ dσ = 0
*
→ (
φ iψ = dα * )
d β * ⎜ ⎟ = dα *cα + d β *cβ = 0
⎝ cβ ⎠

Finally, we’d like to be able to act operators on our states in matrix

mechanics, so that we can compute average values, solve eigenvalue
equations, etc. To understand how we should represent operators, we note
that in wave mechanics operators turn a wavefunction into another
wavefunction. For example, the momentum operator takes one wavefunction
and returns a new wavefunction that is the derivative of the original one:
p̂ dψ
ψ ( x ) ⎯⎯ → (x)
dx
Thus, in order for operators to have the analogous behavior in matrix
mechanics, operators must turn vectors into vectors. As it turns out this is
the most basic property of a matrix: it turns vectors into vectors. Thus we
have our final rule: Operators are represented by matrices.

As an illustration, the Ŝz operator will be represented by a 2x2 matrix in

spin space:
⎛? ?⎞
Ŝz → Sz ≡ ⎜ ⎟
⎝? ?⎠
We have yet to determine what the elements of this matrix are (hence the
question marks) but we can see that this has all the right properties: vectors
are mapped into vectors:
⎛ ? ? ⎞ ⎛ cα ⎞ ⎛ cα ' ⎞
Ŝzψ = ψ ′ → ⎜ ⎟⎜ ⎟ = ⎜ ⎟
⎝ ? ? ⎠ ⎝ c β ⎠ ⎝ cβ ' ⎠
and average values are mapped into numbers
⎛ ? ? ⎞ ⎛ cα ⎞
∫ψ Ŝ ψ dσ
*
z → ( cα *
)
cβ * ⎜ ⎟⎜ ⎟
⎝ ? ? ⎠ ⎝ cβ ⎠

Now, the one challenge is that we have to determine which matrix belongs to
a given operator – that is, we need to fill in the question marks above. As an
exercise, we will show how this is done by working out the matrix
representations of Ŝ 2 , Ŝz , Ŝx and Ŝy .

We’ll start with Ŝ 2 . We know how Ŝ 2 acts on the α and β wavefunctions:

3 3
Ŝ 2α = � 2α Ŝ 2 β = � 2 β
4 4
5.61 Physical Chemistry 24 Pauli Spin Matrices Page 4

Now represent Ŝ 2 as a matrix with unknown elements.

⎛c d ⎞
S2 = ⎜ ⎟
⎝e f ⎠
In wave mechanics, operating Ŝ 2 on α gives us an eigenvalue back, because α
is and eigenfunction of Ŝ 2 (with eigenvalue 34 � 2 ). Translating this into matrix
�
mechanics, when we multiply the matrix S 2 times the vector α , we should
�
get the same eigenvalue back times α :
3 � 3 �
Ŝ 2α = � 2α → S 2α = � 2α
4 4
In this way, instead of talking about eigenfunctions, in matrix mechanics we
�
talk about eigenvectors and we say that α is an eigenvector of S 2 .

We can use this information to obtain the unknown constants in the matrix
S2 :
3 � 3 � ⎛c d ⎞⎛1⎞ 3 2 ⎛1⎞
Ŝ 2α = � 2α → S 2α = � 2α ⇒ ⎜ ⎟⎜ ⎟ = 4 � ⎜ ⎟
4 4 ⎝e f ⎠⎝0⎠ ⎝0⎠
⎛ c ⎞ ⎛ 3 �2 ⎞
⇒⎜ ⎟=⎜4 ⎟
⎝e⎠ ⎝ 0 ⎠
so
c = 43 � 2 e=0
Operating on β
3 2 � 3 � ⎛c d ⎞⎛0⎞ 3 2 ⎛0⎞
Ŝ 2 β = �β → S 2α = � 2α ⇒ ⎜ ⎟⎜ ⎟ = 4 � ⎜ ⎟
4 4 ⎝e f ⎠⎝1⎠ ⎝1⎠
⎛d⎞ ⎛ 0 ⎞
⇒⎜ ⎟=⎜3 2⎟
⎝ f ⎠ ⎝4� ⎠
Thus:
d=0 f = 34 � 2
So for S 2 we have
3 ⎛1 0⎞
S2 = �2 ⎜
4 ⎝ 0 1 ⎟⎠
We can derive Sz in a similar manner. We know its eigenstates as well:
Ŝzα = �2 α Ŝz β = − �2 β
So that the matrix must satisfy:
5.61 Physical Chemistry 24 Pauli Spin Matrices Page 5

� ⎛c d ⎞⎛1⎞ � ⎛1⎞
Ŝzα = α → ⎜e f ⎟⎜0⎟ = 2 ⎜0⎟
2 ⎝ ⎠⎝ ⎠ ⎝ ⎠
⎛c⎞ ⎛ ⎞
�
⇒⎜ ⎟=⎜2⎟
⎝e⎠ ⎝0⎠
which gives us
�
c= e=0
2
Analogous operations on β give
� ⎛c d ⎞⎛0⎞ ⎛0⎞
Ŝz β = − β → ⎜ ⎟⎜ ⎟ = − 2 ⎜ ⎟
�
2 ⎝e f ⎠⎝1⎠ ⎝1⎠
⎛d⎞ ⎛ 0 ⎞
⇒⎜ ⎟=⎜ �⎟
⎝ f ⎠ ⎝− 2 ⎠
�
d=0 f =−
2
Compiling these results, we arrive at the matrix representation of Sz :
� ⎛1 0 ⎞
Sz = ⎜
2 ⎝ 0 −1 ⎟⎠
Now, we need to obtain S x and S y , which turns out to be a bit more tricky.
We remember from our operator derivation of angular momentum that we
can re­write the S x and S y in terms of raising and lowering operators:
1 1
Sx = ( S + + S- ) Sy = (S+ − S- )
2 2i
where we know that
Ŝ+ β = c+α Ŝ+α = 0 and Ŝ−α = c− β Ŝ− β = 0
where c+ and c­ are constants to be determined. Therefore for the raising
operator we have
⎛ c d ⎞ ⎛ 0 ⎞ ⎛ c+ ⎞ ⎛c d ⎞⎛1⎞ ⎛0⎞
Ŝ+ β = c+α → ⎜e f ⎟⎜1⎟ = ⎜ 0 ⎟ Ŝ+α = 0 → ⎜e f ⎟⎜0⎟ = ⎜0⎟
⎝ ⎠⎝ ⎠ ⎝ ⎠ ⎝ ⎠⎝ ⎠ ⎝ ⎠
⇒ d = c+ f = 0 ⇒c=0 e=0
And for the lowering operator
⎛c d ⎞⎛1⎞ ⎛ 0 ⎞ ⎛c d ⎞⎛0⎞ ⎛0⎞
Ŝ−α = c− β → ⎜e f ⎟⎜0⎟ = ⎜c ⎟ Ŝ− β = 0 → ⎜e f ⎟⎜1⎟ = ⎜0⎟
⎝ ⎠⎝ ⎠ ⎝ − ⎠ ⎝ ⎠⎝ ⎠ ⎝ ⎠
⇒ c = 0 e = c− ⇒d=0 f =0
Thus
⎛0 1⎞ ⎛0 0⎞
S + = c+ ⎜ ⎟ S - = c− ⎜ ⎟
⎝0 0⎠ ⎝1 0⎠
5.61 Physical Chemistry 24 Pauli Spin Matrices Page 6

Therefore we find for S x and S y

1⎛ 0 c+ ⎞ 1⎛ 0 −ic+ ⎞
Sx = 1
(S+ + S− ) = ⎜ Sy = 1
(S+ − S− ) =
2
2 ⎝ c− 0 ⎟⎠ 2i ⎜
2 ⎝ ic− 0 ⎟⎠
Thus, we just need to determine the constants: c+ and c­. We do this by
using two bits of information. First, we note that S x and S y are observable,
so they must be Hermitian. Thus,
*
* ⎛ 0 1
c+ ⎞ ⎛ 0 ⎞ ⎛ ⎛ 0 1
c+ ⎞ ⎛ 1 ⎞ ⎞
∫ α * Ŝ β dσ = ( ∫ β * Ŝ α dσ ) (1 0 ) ⎜ 1 = ⎜ ( 0 1) ⎜ 1
2 2
→ ⎟ ⎟
x x
⎝ 2 c−
⎜
0 ⎠⎝1⎠ ⎝ ⎟
⎝ 2 c− 0 ⎟⎠ ⎜⎝ 0 ⎟⎠ ⎠
⇒ c + = c− *
This result reduces our work to finding one constant (c+) in terms of which
we have
1⎛ 0 c ⎞ 1 ⎛ 0 −ic+ ⎞
Sx = ⎜ * + ⎟ Sy = ⎜ *
2 ⎝ c+ 0⎠ 2 ⎝ ic+ 0 ⎟⎠
Note that S x and S y have the interesting property that they are equal to
their adjoints:
†
1⎛ 0
†
c+ ⎞ 1 ⎛ 0 c+ ⎞
Sx = ⎜ * ⎟ = ⎜ ⎟ = Sx
2 ⎝ c+ 0 ⎠ 2 ⎝ c+ * 0⎠
†
1⎛ 0
−ic+ ⎞ 1 ⎛ 0 −ic+ ⎞
†
Sy = ⎜ *⎟ = ⎜ ⎟ = Sy
0 ⎠ 2 ⎝ ic+ *
2 ⎝ ic+ 0 ⎠
This property turns out to be true in general: Hermitian operators are
represented by matrices that are equal to their own adjoint. These self­
adjoint matrices are typically called Hermitian matrices for this reason, and
the adjoint operation is sometimes called Hermitian conjugation.

To determine the remaining constant, we use the fact that S 2 = S x 2 + S y 2 + S z 2 .

Plugging in our matrix representations for S x , S y , Sz and S 2 we find:
3� 2 ⎛ 1 0 ⎞ � 2 ⎛ 1 0 ⎞ ⎛ 1 0 ⎞ 1 ⎛ 0 c+ ⎞ ⎛ 0 c+ ⎞ 1 ⎛ 0 −ic+ ⎞ ⎛ 0 −ic+ ⎞
= + ⎜ ⎟⎜ ⎟+ ⎜ ⎟⎜ ⎟
4 ⎜⎝ 0 1 ⎟⎠ 4 ⎝⎜ 0 −1 ⎟⎠ ⎜⎝ 0 −1 ⎟⎠ 4 ⎝ c+ * 0 ⎠ ⎝ c+ * 0 ⎠ 4 ⎝ ic+ * 0 ⎠ ⎝ ic+ * 0 ⎠
2 2
� 2 ⎛ 1 0 ⎞ c + ⎛ 1 0 ⎞ c+ ⎛ 1 0 ⎞
= ⎜ + +
4 ⎝ 0 1 ⎟⎠ 4 ⎜⎝ 0 1 ⎟⎠ 4 ⎝⎜ 0 1 ⎟⎠
2 2
3 � 2 c+ c
⇒ �2 = + + +
4 4 4 4
2
⇒ c+ = � 2
⇒ c+ = �
5.61 Physical Chemistry 24 Pauli Spin Matrices Page 7

where on the last line, we have made an arbitrary choice of the sign of c+ .
Thus we arrive at the final expressions for S x and S y
� ⎛0 1⎞ � ⎛ 0 −i ⎞
⎜ Sx =
⎟ Sy = ⎜
2 ⎝1 0⎠ 2 ⎝ i 0 ⎟⎠
In summary, then, the matrix representations of our spin operators are:
� ⎛0 1⎞ � ⎛ 0 −i ⎞ � ⎛1 0 ⎞ 3 2 ⎛1 0⎞
Sx = Sy = Sz = S2 = �
2 ⎜⎝ 1 0 ⎟⎠ 2 ⎜⎝ i 0 ⎟⎠ 2 ⎝⎜ 0 −1 ⎟⎠ 4 ⎜⎝ 0 1 ⎟⎠
Given our representations of S x , S y and Sz now we can work out any property
we like by doing some linear algebra. For example, we can work out the
commutator of S x and S y :
� ⎛ 0 1 ⎞ � ⎛ 0 −i ⎞ � ⎛ 0 −i ⎞ � ⎛ 0 1 ⎞
⎡⎣S x ,S y ⎤⎦ = S x S y − S yS x = ⎜ −
2 ⎝ 1 0 ⎟⎠ 2 ⎜⎝ i 0 ⎟⎠ 2 ⎜⎝ i 0 ⎟⎠ 2 ⎜⎝ 1 0 ⎟⎠
� 2 ⎡⎛ 0 1 ⎞ ⎛ 0 −i ⎞ ⎛ 0 −i ⎞ ⎛ 0 1 ⎞ ⎤
= ⎢⎜ ⎟⎜ ⎟−⎜ ⎟⎜ ⎟⎥
4 ⎣⎝ 1 0 ⎠ ⎝ i 0 ⎠ ⎝ i 0 ⎠ ⎝ 1 0 ⎠ ⎦
�2 ⎡⎛ i 0 ⎞ ⎛ −i 0 ⎞ ⎤ � 2 ⎛ i 0 ⎞
= ⎢⎜ ⎟−⎜ ⎟⎥ = ⎜ ⎟
4 ⎣⎝ 0 −i ⎠ ⎝ 0 i ⎠ ⎦ 2 ⎝ 0 −i ⎠
⇒ ⎡⎣S x ,S y ⎤⎦ = i�S z
It is comforting to see that the matrices that represent the angular
momentum operators obey the commutation relations for angular momentum!
It is similarly possible to work out the eigenvalues of Ŝ 2 , Ŝz and Ŝx by
computing the eigenvalues of S x , S y and Sz ; average values can be obtained
by taking (row)*x(matrix)x(column) products. We are thus in a position to
compute anything we want for these operators. As it turns out, any operator
in this 2x2 space can be written as a linear combination of S x , S y , Sz and S2 .
So, in some sense, we now have all the information we could possibly want
about spin­½ systems.

In honor of Pauli, it is conventional to define the dimensionless versions of

S x , S y , Sz (i.e. matrices without the leading factor of � / 2 ) as Pauli Spin
matrices:
⎛ 0 1⎞ ⎛ 0 −i ⎞ ⎛1 0⎞
σx ≡ ⎜ ⎟ σy ≡ ⎜ ⎟ σz ≡ ⎜ ⎟
⎝ 1 0⎠ ⎝i 0⎠ ⎝ 0 −1⎠
One of the reasons the Pauli spin matrices are useful (or equivalently the
matrix representations of S x , S y and Sz ) is that they are the simplest
5.61 Physical Chemistry 24 Pauli Spin Matrices Page 8

possible place to practice our skills at using matrix mechanics. We will see
later on that more complicated systems can also be described by matrix­
vector operations. However, in these cases the matrices will have many
more elements – sometimes even infinite numbers of elements! Therefore, it
is best to get some practice on these simple 2x2 matrices before taking on
the more complicated cases.