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221A Lecture Notes: Spherical Harmonics 1 Oribtal Angular Momentum
221A Lecture Notes: Spherical Harmonics 1 Oribtal Angular Momentum
Spherical Harmonics
1
(2)
When using the position representation, the action of the angular momentum on any state is given by a differential operator
h
~
h
~
~
h~x|L|i
= ~x h~
x|i = ~x (~
x).
i
i
(3)
(5)
(6)
r x r y r z
x
r
= x y z y
x y z
z
sin cos
sin sin
cos
x
(7)
x
r sin2 cos sin cos cos sin
r
1
2
cos
y =
r sin sin sin cos sin
. (8)
r sin
z
r sin cos
sin2
0
!
h
Ly =
cos cot sin
,
i
h
.
Lz =
i
It is useful to take the combinations
!
h
i
L = e
i cot
.
i
(9)
(10)
(11)
(12)
Finally,
"
L =
h
sin
sin
h2
h2 2
p~2
=
(x + y2 + z2 ) =
2m
2m
2m
1 2
+
.
sin2 2
2
2
+
2
r
r r
~2
L
.
2mr2
(13)
(14)
Looking at the expression for Lz , you can see that it is of the same form
as the momentum operator of a particle on a circle, whose eigenvalues are
quantized as n
h for n Z. Therefore, Lz is also quantized as m
h for m Z.
An immediate consequence is that no half-odd values are allowed for Lz , and
hence half-odd j cannot be obtained for orbital angular momentum. Only
integer j is possible.
2
Spherical Harmonics
(15)
(16)
The spherical harmonics are defined as the wave functions of angular momentum eigenstates
Ylm (, ) = h, |l, mi.
(17)
Sakurai uses the notation h~n| and call them direction eigenkets.
Clearly, the defintions of angular momemum eigenstates
~ 2 |l, mi = l(l + 1)
L
h2 |l, mi,
Lz |l, mi = m
h|l, mi,
(18)
(19)
1
sin
sin
1 2
+
Ylm = l(l + 1)
h2 Ylm ,
2
2
sin
h
m
Y
= m
hYlm .
i l
#
(20)
(21)
The latter equation is easy to solve: the azimuth dependence of the spherical
harmonics must be eim . But figuring out the polar angle dependence needs
more work. The rest of the discussion here is on this issue.
Both in the case of the harmonic oscillator and the Landau levels (energy
levels of a charged particle in a uniform magnetic field), it was useful to write
down an equation for the ground state of the form a|0i = 0. It was useful
because it gave us a linear differential equation instead of a quadratic one
(e.g., Schrodinger equation). The linear differential equations are far easier
to solve. We can take the same strategy for the spherical harmonics.
2.1
Y l (, ) = 0.
0 = h, |L |l, li = ei i cot
i
(22)
h
l
Y
i l
(23)
(25)
(26)
f () = c sinl
(27)
Therefore,
with an overall normalization constant c.
Putting things together, we find
Yll (, ) = c sinl eil .
4
(28)
1=
l 2
d|Yl | =
d cos
d|c|2 sin2l .
(29)
1 = 2|c|
dx(1 x2 )l ..
(30)
1 = 2|c|
2 2l+1
dt tl (1 t)l .
(31)
dt tp1 (1 t)q1 =
(p)(q)
.
(p + q)
(32)
Therefore,
1 = 2|c|2 22l+1
(l + 1)(l + 1)
l!l!
= 4|c|2 22l
.
(2l + 2)
(2l + 1)!
We find
(33)
1 (2l + 1)!
.
(34)
|c| = l
2 l!
4
The phase of c is fixed by picking a convention. The commonly used
convention (the same as Sakurais) is not to have an additional phase factor
1
Yll (, ) = l
2 l!
(2l + 1)!
sinl eil .
4
(35)
Now that we know Yll , we can keep acting L+ on it to obtain all Ylm .
Recall that the general discussion of angular momentum taught us that
L+ |l, mi =
Then we find
1
1
q
Ylm (, ) = q
h
(l + m)(l m + 1) h
(l + m 1)(l m + 2)
"
h
i
q
q
e
i cot
h
(2)(l + l 1) h
(1)(l + l) i
1
v
u
u
= t
"
(l m)!
ei
+ i cot
(2l)!(l + m)!
!#l+m
Yll (, )
!#l+m
Yll (, )
(37)
v
u
(2l + 1)! u
t (l m)! eim d (m 1) cot
4
(2l)!(l + m)!
d
!
d
d
(m 2) cot
+ (l 1) cot
d
d
=
v
u
1 u
t (2l + 1)(l m)! eim
2l l!
4(l + m)!
d
(m 1) cot
d
d
d
(m 2) cot
+ (l 1) cot
d
d
d
+ l cot sinl .
d
!
d
+ l cot sinl .
d
(38)
d
1 d
+ k cot =
sink
d
sink d
(39)
Then
v
u
d
1
d
sin(m2)
sinl1
l1
(m2) d
d
sin
sin
1 d
sinl sinl
sinl d
=
=
=
v
u
1 u
t (2l + 1)(l m)! eim sinm
2l l!
4(l + m)!
v
u
1 u
t (2l + 1)(l m)! eim sinm
2l l!
4(l + m)!
1 d
sin d
!l+m
d cos
sin2l
!l+m
sin2l
l+m
t (2l + 1)(l m)! eim (1 x2 )m/2 d
(1 x2 )2l .
l+m
l+m u
u
(1)
2l l!
4(l + m)!
(40)
dx
2.2
Legendre Polynomials
l+m
(1)l
2 m/2 d
(1
x
)
(1 x2 )l .
(43)
2l l!
dxl+m
This expression allows you to pick m < 0.
Plm is called associated Legendre polynomials, and Plm (x) = Pl (x). The
definitions look complicated, but they are just polynomials! Pl is a polynomial of order l. Plm has this funny factor (1 x2 )m/2 with a fractional power,
but we will set x = cos in the end, and (1 x2 )m/2 = sinm . Remember is
the polar angle, and we only consider 0 so that sin 0. Therefore,
Plm is a polynomial of order m in sin and l m in cos .
Now let us prove a surprising identity
Plm (x) =
(l m)! m
P (x).
(l + m)! l
l+m
(44)
d
2 l
m
Let us start with dx
l+m (1 x ) for m > 0 which appears in Pl (x). We
dlm
2 l
expand it out and see how it can be related to dx
lm (1 x )
dl+m
dl+m
2 l
(1
x
)
=
(1 x)l (1 + x)l
dxl+m
dxl+m
7
l+m
X
l+m Cr
r=0
dr
(1 x)l
dxr
dl+mr
(1 + x)l . (45)
dxl+mr
Even though the sum extends for 0 r l + m, the term in the first
parentheses vanishes for r > l while the second for l + m r > l. Therefore,
the sum is taken only for m r l. Then
dl+m
(1 x2 )l
l+m
dx
l
X
l!
(1)r l!
(1 x)lr
(1 + x)rm
=
l+m Cr
(l r)!
(r m)!
r=m
=
lm
X
s=0
l+m Cm+s
(1)m+s l!
l!
(1 x)lms (1 + x)s .
(l m s)!
s!
(46)
lm
X
1
(l + m)!
(1)m+s l!
l!
(1 x)ls (1 + x)m+s
2
m
(1 x ) s=0 (m + s)!(l s)! (l m s)!
s!
lm
X
1
(l + m)! (1)m+s l!
l!
(1 x)ls
(1 + x)m+s
2
m
(1 x ) s=0 s!(l m s)! (l s)!
(m + s)!
lm
X
(l + m)!
(l m)!
1
(1)m+s
2
m
(l m)! (1 x ) s=0 s!(l m s)!
ds
(1)s s (1 x)ls
dx
dlms
(1 + x)m+s
dxlms
X
(l + m)! (1)m lm
ds
=
(1 x)ls
lm Cs
2
m
s
(l m)! (1 x ) s=0
dx
dlms
(1 + x)m+s
lms
dx
(47)
(1)l
(1
2l l!
x2 )m/2 , we find
l+m
(1)l
2 m/2 d
(1
x
)
(1 x2 )l
2l l!
dxl+m
(1)l
(l + m)!
dlm
1
(1)m l
(1 x2 )l
(l m)!
2 l! (1 x2 )m/2 dxlm
(l + m)!
=
(1)m Plm (x).
(l m)!
(48)
2 (l + m)!
n,l .
2l + 1 (l m)!
(49)
n+m
(1)n
2 m/2 d
dx
=
(1
x
)
(1 x2 )n
n
n+m
2 n!
dx
1
!
l
l+m
(1)
2 m/2 d
2 l
(1 x )
(1 x )
2l l!
dxl+m
!
!
(1)n+l Z 1
dn+m
dl+m
2 m
2 n
2 l
= n+l
dx(1 x )
(1 x )
(1 x ) .(50)
2 n!l! 1
dxn+m
dxl+m
Z 1
l+m
dl+m
(1)l+l
l+m
2 l
2 m d
dx(1
x
)
=
(1)
(1
x
)
(1 x2 )l
l+m
l+m
2l+l l!l!
dx
dx
1
Z 1
l+m
(1)l+l
dl+m
l+m
2 l
m 2 m d
=
(1)
dx(1
x
)
(1)
(x
)
(1)l (x2 )l
l+m
l+m
2l+l l!l!
dx
dx
1
!
Z 1
dl+m 2 m (2l)! lm
1
2 l
dx(1 x )
x
(x )
= 2l
2 l!l! 1
dxl+m
(l m)!
1 Z1
(2l)!
= 2l
dx(1 x2 )l (l + m)!
.
(51)
2 l!l! 1
(l m)!
!
1 (2l)!(l + m)! Z 1
2dt(2t(2 2t))l
2l
2 l!l! (l m)!
0
Z 1
2 (2l)!(l + m)!
dttl (1 t)l
l!l! (l m)!
0
2 (2l)!(l + m)! (l + 1)(l + 1)
l!l! (l m)!
(2l + 2)
2
(2l)!(l + m)!
(2l + 1)! (l m)!
2 (l + m)!
2l + 1 (l m)!
=
=
=
=
=
2.3
(52)
v
u
u
m t (2l + 1)(l m)! im m
= (1)
e Pl (cos ).
4(l + m)!
(53)
(2l + 1)
Pl (cos ).
(54)
4
When m < 0, an alternative expression is obtained by using the identity
Eq. (44),
Yl 0 =
Yl m
v
u
u (2l + 1)(l |m|)!
|m|
= t
eim Pl (cos ).
4(l + |m|)!
(55)
(56)
2.4
dYlm ()(Ylm
0 ())
m+m0
= (1)
v
v
u
u
u (2l + 1)(l m)! u (2l0 + 1)(l0 m0 )!
t
t
4(l0 + m0 )!
4(l + m)!
d cos
im im
e
.
dPlm (cos )Plm
0 (cos )e
(57)
= 2m,m
4(l0 + m)!
4(l + m)!
v
v
u
u
u (2l + 1)(l m)! u (2l0 + 1)(l0 m)!
t
t
0
= 2m,m
4(l0
4(l + m)!
= 2m,m0 l,l0
+ m)!
dxPlm (x)Plm
0 (x)
2 (l + m)!
l,l0
2l + 1 (l m)!
= m,m0 l,l0 .
(58)
m
d(Ylm
0 ) Yl . (59)
Ylm (, )(Ylm (0 , 0 )) .
(60)
l,m
Here,
( 0 )
( 0 ).
( ) = (cos cos )( ) =
sin
2
11
(61)
2.5
Examples
Y10 =
s
Y22
(63)
3
cos ,
4
(64)
15
sin2 e2i ,
32
(65)
Y21 =
(62)
15
sin cos ei ,
8
(66)
5
(3 cos2 1).
(67)
16
In spectroscopic symbols, l = 0, 1, 2, 3, 4, correspond to s, p, d, f, g,
orbitals.
In chemistry and solid-state physics, you see symbols like px , dx2 y2 . They
refer to certain linear combinations of spherical harmonics. The general rule
is to first multiply the spherical harmonics by rl , and you find
1
(68)
Y00 = ,
4
s
3
rY11 =
(x iy),
(69)
8
Y20
rY10
=
s
r2 Y22 =
3
z,
4
(70)
15
(x iy)2 ,
32
(71)
Y21
=
s
r2 Y20 =
15
(x iy)z,
8
(72)
5
(3z 2 r2 ).
16
(73)
s for sharp, p for principal, d for diffuse, f for fundamental, and the rest is just
alphabetical.
12
1
1
while px to (Y11+ Y11 )/ 2 and py to (Y
1 Y1 )/i 2. dx2 y 2 corresponds
1
2
to (Y22 + Y2 )/ 2, dyz to (Y21 Y2 )/i 2.
Im sure you have seen shapes of spherical harmonics in textbooks. It
is important to understand what they actually are. In many cases, what is
shown is a surface given by points
r = |Ylm (, )|2 .
(74)
In other words, the distance of the surface from the origin along a direction
is determined by the probability of finding the particle along that direction.
They actually do not represent the shapes of the wave function. They just
show along which direction the probability is big or small.
In certain cases, though, these plots do represent the shapes of the
actual wave function. Remember that the actual wave function has the radial
wave function on top of the spherical harmonics. Suppose the radial wave
function is a smoothly decaying function, say, er/a0 . Now you try to draw a
surface of constant probability density in three dimensions. Then along the
directions where |Ylm |2 is larger, the constant probability is attained even at
higher r; but along the directions with small |Ylm |2 , you need to go closer
to the origin to get the same probability density. Then the plot mentioned
above can approximate the shape of the actual wave function. But if
you want to interpret the plots in this manner, it obviously depends on the
details of the radial wave function, and what value you chose for the surface of
constant probability density. Just presenting the shapes of, say, pz orbitals
independent of n (the principal quantum number) is therefore misleading.
2.6
Mathematica
It is useful to know that Mathematica has built-in commands for the spherical harmonics SphericalHarmonicY[l,m,,] for Ylm (, ), the Legendre
polynomials LegendreP[n,x] for Pn (x), and the associated Legendre polynomials LegendreP[n,m,x] for Pnm (x).
13