4.

The Hydrogen Atom

spectrum of atomic hydrogen

electric discharge through hydrogen gas; molecules

are dissociated and excited atoms emit light

spectrum has discrete lines

[Figure: spectrum of atomic hydrogen, Atkins 9th ed., Fig. 9.1]

PChem II 4.1
lines in the visible region: Balmer series

µ ¶
1 1 1
ν̃ = = R H 2 − 2 , n = 3, 4, . . .
λ 2 n

R H = 109677 cm−1 Rydberg constant for hydrogen

further series of lines discovered later:

Lyman series: ultraviolet
Paschen series: infrared

general fit for spectral lines

à !
1 1 1
ν̃ = = RH 2 − 2 , n 2 = n 1 + 1, n 1 + 2, . . .
λ n1 n2

n 1 = 1: Lyman
n 1 = 2: Balmer
n 1 = 3: Paschen

goal: understand the line spectrum

hydrogen atom = proton + electron

PChem II 4.2
six degrees of freedom

wavefunction has six arguments, three spatial coor-

dinates for the nucleus, ~x N = (x N , y N , z N ), and three
spatial coordinates for the electron, ~ x e = (x e , y e , z e )
consider the more general case of hydrogen-like or
hydrogenic atoms: nucleus with atomic number Z
and one electron

single hydrogen-like atom in empty space

Ĥtotψ(~ x e ) = E totψ(~
x N ,~ x N ,~
xe )
ħ2 2 ħ2 2
Ĥtot = − ∇N − ∇e + V (r )
2m N 2m e
∂2 ∂2 ∂2
∇2N = 2
+ +
∂x N ∂y N2 2
∂z N
2 2
∂ ∂ ∂2
∇2e = + +
∂x e2 ∂y e2 ∂z e2
Ze ·e 1
V (r ) = −
4π²0 r

r distance of electron from nucleus

PChem II 4.3
²0 = 8.854 × 10−12 J−1C2m−1 vacuum permittivity

central theorem of mechanics: motion of a complex

system = motion (translation) of the center of mass
plus motion around the center of mass

ħ2 2 ħ2 2
Ĥtot = − ∇c.m. − ∇ + V (r )
2m 2µ

m = m N + m e total mass

1 1 1
= + , µ reduced mass
µ m N me
m N À m e =⇒ µ u m e , ~
x c.m. u ~
x N and ~
x u~
xe
ψ(~ x e ) = ψ(~
x N ,~ x c.m.,~
x)
Ĥtot = Ĥc.m. + Ĥ
E tot = E c.m. + E

separation of variables

ψ(~ x ) = ψc.m.(~
x c.m.,~ x c.m.)ψ(~
x)
Ĥc.m.ψc.m. = E c.m.ψc.m.

PChem II 4.4
Schrödinger equation for a free particle

x c.m.) ∼ exp(i~
ψc.m.(~ k ·~
x c.m.)

Ĥ ψ(~
x ) = E ψ(~
x)
Schrödinger equation for internal degrees of freedom

ħ2 2 Z e2 1
− ∇ ψ− ψ = Eψ
2µ 4π²0 r

2 Z e 2µ 1 2µE
∇ ψ+ 2
ψ=− 2 ψ
2π²0ħ r ħ
γ
∇2ψ + ψ = ²ψ
r
Z e 2µ 2µE
γ≡ 2
, ²≡−
2π²0ħ ħ2
[²] = (kg J)/(J2 s2) = kg/(kg m2s−2s2) = 1/m2

Coulomb potential: spherical symmetry =⇒ spherical

coordinates

2 1 ∂2 1 2 1 ∂ 2∂ 1 2
∇ = r + 2Λ = 2 r + 2Λ
r ∂r 2 r r ∂r ∂r r

PChem II 4.5
 2 1 ∂2 1 ∂ ∂
Λ = + sin θ
2
sin θ ∂φ2
sin θ ∂θ ∂θ
1 ∂2 1 2 γ
r ψ + 2 Λ ψ + ψ = ²ψ
r ∂r 2 r r

Coulomb potential has no angular dependence =⇒

separation of variables

ψ(r, θ, φ) = R(r )Y (θ, φ)

à !
2
1 ∂ 1 2 γ
r R Y + 2 RΛ Y + RY = ²RY
r ∂r 2 r r
2
multiply on both sides by r /(RY )
2
1 d 1 2
r2 r R + Λ Y + γr = ²r 2
r R dr 2 Y
=⇒
1 2
Λ Y = const
Y
and

2 1 d2 2
r r R + γr − ²r = −const
r R dr 2

PChem II 4.6
Λ2Y = const Y , 3-D rigid rotor
−l (l + 1) ≡ const
Λ2Y = −l (l + 1)Y
Yl ,ml (θ, φ) = Θl ,ml (θ)Φml (φ)

2
1 d
r2 r R + γr − ²r 2
= l (l + 1)
r R dr 2
d2 γ l (l + 1)
µ ¶
2
rR + − 2
r R = ²r R radial wave equation
dr r r
x x
 
 
Coulomb potential effective potential, centripetal force

solve the radial wave equation

large r :

d2
2
r R = ²r R
dr
(r R 0 + R)0 = r R 00 + 2R 0 = ²r R
r R 00 = ²r R for large r

PChem II 4.7
R 00 = ²R
p
R(r ) ∼ exp(− ²r )
p
R(r ) = f (r ) exp(− ²r )
nondimensionalize:
% γ
r= p , n≡ p
2 ² 2 ²
f (%) ≡ %l L(%)
insert into radial wave equation
00
¤ 0
L (%) + 2(l + 1) − % L (%) + [n − (l + 1)] L(%) = 0
£

associated Laguerre equation

acceptable solutions if
n = 1, 2, . . . and 0 ≤ l ≤ n − 1
γ
n = p =⇒
2 ²
Z 2e 4µ 1
En = −
32π2²20ħ 2 n 2

E < 0: bound states

PChem II 4.8
E = 0: electron at ∞ and at rest: V (∞) = 0

R n,l (%) = %l L n,l (%) exp(−%/2) (see 4.25 for R n,l up to (3, 2))

L n,l associated Laguerre polynomials

s
p 2µE
% = 2 ²r = 2 − 2
r
ħ
µZ e 2 r
=2
4π²0ħ2 n
µ me e 2 r
= 2Z
m e 4π²0ħ2 n
me a0
r =n %
µ 2Z
4π²0ħ2
a0 = 2
= 52.9177 pm Bohr radius
me e
a0
µ u me ⇒ r = n %
2Z
2Z
ρ≡ r
a0

besides the discrete spectrum, the Schrödinger equa-

PChem II 4.9
tion for hydrogenic atoms also has a continuous part:

E ≥ 0: nucleus plus free electron; atom has been com-

pletely ionized

three quantum numbers for bound states:

principal quantum number: n = 1, 2, . . .

energy level, radial wavefunction


azimuthal quantum number: 

l = 0, 1, 2, . . . , n − 1 


angular wavefunction

magnetic quantum number:  


m l = −l , −l + 1, . . . , l − 1, l 

energy: E n , no dependence on l and m l

energy levels are degenerate, except n = 1, ground
state

ψn,l ,ml (r, θ, φ) = R n,l (r )Yl ,ml (θ, φ) = R n,l (r )Θl ,ml (θ)Φml (φ)

atomic orbital

PChem II 4.10
by definition, an orbital depends on the spatial coor-
dinates of one and only one electron

hydrogen atom

e 4µ 1
En = −
32π2²20ħ2 n 2
hcR H e 4µ
En = − 2
, hcR H ≡
n 32π2²20ħ2
E 1 = −hcR H
1
En = E1
n2

PChem II 4.11
[Figure: energy levels of hydrogen atom, Atkins 9th ed., Fig. 9.5]

PChem II 4.12
spectrum of atomic hydrogen
à !
hcR H hcR H ¯ ¯
E n2 − E n1 = − − − , hν = E n2 − E n1 ¯
¯
n 22 n 12
¯ ¯
1 ν ¯ R H R H ¯¯
¯
ν̃ = = = ¯ 2 − 2 ¯
λ c ¯ n1 n2 ¯

agrees with experiments =⇒ we have calculated

RH

e 4µ
RH =
32π2²20ħ2hc
1 1 1 1 1
= + = +
µ m p m e 1.67262 × 10−27 kg 9.10938 × 10−31 kg
µ = 9.10444 × 10−31 kg
4π²0 = 1.11265 × 10−10 J−1C2m−1
(1.602176 × 10−19 C)4 · 9.10444 × 10−31 kg
RH = −10 −1 2 −1 2 −34 2
×
2 (1.11265 × 10 J C m ) (1.05457 × 10 J s)
1
6.62608 × 10−34 J s · 2.997925 × 108 m s−1

PChem II 4.13
R H = 1.09678 × 107 m−1 = 1.09678 × 105 cm−1

−1
experimental value: R H = 109677 cm

ionization energy: electron goes from ground state,

E 1 = −hcR H to the lowest unbound state, E ∞ = 0:

I = hcR H = −E 1 = 2.17869 × 10−18 J = 13.598 eV

shell: orbitals with the same value of n

n = 1 2 3 4 ...
K L M N ...
subshell: orbitals with the same value of n and value
of l
l = 0 1 2 3 4 5 6 ...
s p d f g h i ...

PChem II 4.14
[Figure: energy levels, shells and subshells, Atkins 9th ed., Fig. 9.7]

[Figure: organization of orbitals into shells and subshells, Atkins 9th ed., Fig. 9.8]

PChem II 4.15
µ = 0.999456m e for H-atom

use µ = m e (exact for hydrogenic atom with infinitely

massive or fixed nucleus)

ground state orbital : n = 1, l = 0, m l = 0

¶3/2
1 Z
µ
ψ100(r, θ, φ) = p exp(−Z r /a 0)
π a0

1s-orbital spherically symmetric; all s-orbitals are

spherically symmetric

¯2
x )} = ψn,l ,ml (~
¯
x e ∈ dτ(~
Prob{~ ¯ x )¯ dτ(~
x)

generally contains radial and angular information; no

angular dependence for s-orbitals

PChem II 4.16
[Figure: probability density, Atkins 9th ed., Fig. 9.12]

often only interested how far the electron is from the

nucleus: volume element dτ = thin spherical shell of
radius r and thickness dr

for s-orbitals

¯ ¯2
Prob{~ x e ∈ shell at r } = ¯ψs¯ 4πr 2dr
¯ ¯2
2¯
P (r ) = 4πr ψs¯ radial distribution function

PChem II 4.17
if the wavefunction is not spherically symmetrical, in-
tegrate over the angles

Z π Z 2π ¯ ¯2 2
¯ψ
P (r )dr = n,l ,m l (r, θ, φ) r sin θdr dθdφ
¯
0 0
Z π Z 2π
P (r )dr = r 2[R n,l (r )]2 Yl∗,ml (θ, φ)Yl ,ml (θ, φ) sin θdθdφ
0 0

P (r ) = r 2[R n,l (r )]2

H-atom: ground state radial distribution function

2 1
P (r ) = 4πr exp(−2r /a 0)
πa 03

P (r ) → 0 as r → ∞: ψ100 → 0 exponentially
P (r ) → 0 as r → 0: ψ100 6→ 0, Vshell → 0

PChem II 4.18
[Figure: radial distribution function, Atkins 9th ed., Fig. 9.13]

most probable radius r 0: P (r 0) =max

¯
dP (r ) ¯¯
=0
dr ¯ r =r 0
2µ ¶
8r 0 −2r 0/a0 4r 0 2 −2r 0/a0
3
e + 3
− e =0
a0 a0 a0
r0
1− = 0 =⇒ r 0 = a 0
a0

PChem II 4.19
n = 2: four orbitals
l = 0: 2s-orbital (ρ = 2Z r /a 0)
¶3/2 µ r
Z
µ ¶
1 1 1
ψ200(r, θ, φ) = p 2 − ρ exp(−ρ/4) ×
2 2 a0 2 4π

ψ100(0, 0, 0) 6= 0, ψ200(0, 0, 0) 6= 0
s-orbitals: electron has a nonzero probability of being
at the nucleus
l = 1: 2p-orbitals
µ ¶3/2 µ ¶1/2
1 Z 3
ψ210(r, θ, φ) = p ρ exp(−ρ/4) × cos θ
4 6 0 a 4π
µ ¶3/2
1 Z
ψ21−1(r, θ, φ) = p ρ exp(−ρ/4)×
4 6 a0
µ ¶1/2
3
(+1) sin θ exp(−iφ)
8π
µ ¶3/2
1 Z
ψ21+1(r, θ, φ) = p ρ exp(−ρ/4)×
4 6 0 a
µ ¶1/2
3
(−1) sin θ exp(+iφ)
8π

PChem II 4.20
p-orbitals: at r = 0: ψp (0, 0, 0) = 0

Prob{e− at nucleus} = 0: centripetal effect

m l = 0: ψ210 ∼ cos θ ⇒ θ = π/2 = x - y -plane = nodal
plane: angular node

ψ2210 lies along the z -axis: 2pz orbital

ψ21−1 ∼ sin θ and ψ21+1 ∼ sin θ : vanish on the z -axis;
ψ21−1 [2p− orbital] and ψ21+1 [2p+ orbital] are complex
and have no further angular nodes

construct real wavefunctions with proper nodal

planes by linear superposition:

1 ¡
2px = − p 2p+ − 2p− ∼ cos φ
¢
2
i ¡
2p y = p 2p+ + 2p− ∼ sin φ
¢
2

lˆz 2pz = 0ħ · 2pz

lˆz 2p− = (−1)ħ · 2p−
lˆz 2p+ = (+1)ħ · 2p+

PChem II 4.21
lˆ22pz = 1 · 2 · ħ2 · 2pz
lˆ22p− = 1 · 2 · ħ2 · 2p−
lˆ22p+ = 1 · 2 · ħ2 · 2p+

lˆz 2px 6= c · 2px , lˆz 2p y 6= c · 2p y

spectroscopic transitions and selection rules

(n 2, l 2, m l 2) −→ (n 1, l 1, m l 1) : ∆E

Bohr frequency condition: |∆E | = hν: conservation of

energy

conservation of angular momentum: photon spin s =

1 =⇒

∆l = ±1, ∆m l = 0, ±1

Ĥtr energy operator for the transition; e.g., for elec-

tric dipole transition, Ĥtr = −~ ~ (t ), where ~
µ·E µ = q~
r =
electric dipole moment and E ~ = electric field

PChem II 4.22
transition is forbidden if
Z
ψ∗n f ,l f ,ml f Ĥtrψni ,l i ,ml i dτ = 0

[Figure: Grotrian diagram, Atkins 9th ed., Fig. 9.17]

~ : 10 times weak-
magnetic dipole transition, Ĥtr ∼ ∇E
5

PChem II 4.23
er than electric dipole transition
8
electric quadrupole transition: 10 times weaker than
electric dipole transition (∆l = 0, ±2)

PChem II 4.24
 Table 1: Hydrogenic Radial Wave
Functions, ρ = 2Z r /a 0 (Differs from
Atkins’ definition of ρ )

n l R n,l (ρ)

¶3/2
Z
µ
1 0 2 exp(−ρ/2)
a0
¶3/2 µ
Z
µ ¶
1 1
2 0 2 − ρ exp(−ρ/4)
2(2)1/2 a0 2
¶3/2
Z
µ
1
2 1 1/2
ρ exp(−ρ/4)
4(6) a0
Z 3/2
¶ µ µ ¶
1 1 2
3 0 1/2 a
6 − 2ρ + ρ exp(−ρ/6)
9(3) 0 9
µ ¶3/2 µ
Z
¶
1 1
3 1 1/2 a
4 − ρ exp(−ρ/6)
27(6) 0 3
µ ¶3/2
1 Z 2
3 2 1/2 a
ρ exp(−ρ/6)
81(30) 0

PChem II 4.25
 Table 2: Spherical Harmonics

l ml Yl ,ml (θ, φ)

µ ¶1/2
1
0 0
4π
µ ¶1/2
3
1 0 cos θ
4π
3 1/2
µ ¶
1 ±1 ∓ sin θ exp(±iφ)
8π
5 1/2
µ ¶
2 0 (3 cos2 θ − 1)
16π
µ ¶1/2
15
2 ±1 ∓ cos θ sin θ exp(±iφ)
8π
µ ¶1/2
15
2 ±2 sin2 θ exp(±2iφ)
32π

PChem II 4.26