CHAPTER 7

The Hydrogen Atom

■ 7.1 Application of the Schrödinger Equation to the

Hydrogen Atom
■ 7.2 Solution of the Schrödinger Equation for Hydrogen
■ 7.3 Quantum Numbers
■ 7.4 Magnetic Effects on Atomic Spectra – The Normal
Zeeman Effect
■ 7.5 Intrinsic Spin
■ 7.6 Energy Levels and Electron Probabilities

The atom of modern physics can be symbolized only through a partial differential
equation in an abstract space of many dimensions. All its qualities are inferential;
no material properties can be directly attributed to it. An understanding of the
atomic world in that primary sensuous fashion…is impossible.

- Werner Heisenberg
7.1: Application of the Schrödinger
Equation to the Hydrogen Atom
■ The approximation of the potential energy of the electron-proton
system is electrostatic:

■ Rewrite the three-dimensional time-independent Schrödinger

Equation.

For Hydrogen-like atoms (He+ or Li++)

■ Replace e2 with Ze2 (Z is the atomic number).

■ Use appropriate reduced mass µ.

Application of the Schrödinger Equation
■ The potential (central force) V(r) depends on the distance r between
the proton and electron.

Transform to spherical polar

coordinates because of the
radial symmetry.
Insert the Coulomb potential
into the transformed
Schrödinger equation.

Equation 7.3
Application of the Schrödinger Equation
■ The wave function ψ is a function of r, θ, .
Equation is separable.
Solution may be a product of three functions.
Equation 7.4

■ We can separate Equation 7.3 into three separate differential

equations, each depending on one coordinate: r, θ, or .
7.2: Solution of the Schrödinger Equation
for Hydrogen
■ Substitute Eq (7.4) into Eq (7.3) and separate the resulting equation
into three equations: R(r), f(θ), and g( ).
Separation of Variables
■ The derivatives from Eq (7.4)

■ Substitute them into Eq (7.3)

■ Multiply both sides by r2 sin2 θ / Rfg

r Equation 7.7
Solution of the Schrödinger Equation

■ Only r and θ appear on the left side and only appears on the right
side of Eq (7.7)
■ The left side of the equation cannot change as changes.
■ The right side cannot change with either r or θ.

■ Each side needs to be equal to a constant for the equation to be true.

Set the constant −mℓ2 equal to the right side of Eq (7.7)

Equation 7.8 -------- azimuthal equation

■ It is convenient to choose a solution to be .

Solution of the Schrödinger Equation
■ satisfies Eq (7.8) for any value of mℓ.
■ The solution must be single valued in order to have a valid
solution for any , which is

■ mℓ to be zero or an integer (positive or negative) for this to be

true.

■ If Eq (7.8) were positive, the solution would not be normalized.

Solution of the Schrödinger Equation

■ Set the left side of Eq (7.7) equal to −mℓ2 and rearrange it.

■ Everything depends on r on the left side and θ on the right side of

the equation.
Solution of the Schrödinger Equation

■ Set each side of Eq (7.9) equal to constant ℓ(ℓ + 1).

----Radial equation
Equation 7.10

----Angular equation
Equation 7.11

■ Schrödinger equation has been separated into three ordinary

second-order differential equations [Eq (7.8), (7.10), and (7.11)],
each containing only one variable.
Solution of the Radial Equation

■ The radial equation is called the associated Laguerre equation

and the solutions R that satisfy the appropriate boundary conditions
are called associated Laguerre functions.

■ Assume the ground state has ℓ = 0 and this requires mℓ = 0.

Eq (7.10) becomes

■ The derivative of yields two terms and V is the Coulomb

potentials.
Write those terms:
Equation 7.13
Solution of the Radial Equation
■ Try a solution
A is a normalized constant.
a0 is a constant with the dimension of length.
Take derivatives of R and insert them into Eq (7.13).

Equation 7.14

■ To satisfy Eq (7.14) for any r is for each of the two expressions in

parentheses to be zero.
Set the second parentheses equal to zero and solve for a0.

Set the first parentheses equal to zero and solve for E.

Both equal to the Bohr result.

Quantum Numbers
■ The appropriate boundary conditions to Eq (7.10) and (7.11)
leads to the following restrictions on the quantum numbers ℓ and
mℓ :
❑ ℓ = 0, 1, 2, 3, . . .
❑ mℓ = −ℓ, −ℓ + 1, . . . , −2, −1, 0, 1, 2, . ℓ . , ℓ − 1, ℓ

t.si
❑ |mℓ| ≤ ℓ and ℓ < 0.

■ The predicted energy level is

o.o
n = 1,2,3…..

n>l
Hydrogen Atom Radial Wave Functions
■ First few radial wave functions Rnℓ

■ Subscripts on R specify the values of n and ℓ.

Solution of the Angular and Azimuthal
Equations
■ The solutions for Eq (7.8) are .
■ Solutions to the angular and azimuthal equations are linked because
both have mℓ.
■ Group these solutions together into functions.

---- spherical harmonics

Normalized Spherical Harmonics
Solution of the Angular and Azimuthal
Equations
■ The radial wave function R and the spherical harmonics Y
determine the probability density for the various quantum
states. The total wave function depends on n, ℓ,
and mℓ. The wave function becomes
7.3: Quantum Numbers
The three quantum numbers:
❑ n Principal quantum number
❑ ℓ Orbital angular momentum quantum number
❑ mℓ Magnetic quantum number

The boundary conditions:

❑ n = 1, 2, 3, 4, . . . Integer
❑ ℓ = 0, 1, 2, 3, . . . , n − 1 Integer
❑ mℓ = −ℓ, −ℓ + 1, . . . , 0, 1, . . . , ℓ − 1, ℓ Integer

The restrictions for quantum numbers:

❑ n>0
❑ ℓ<n
❑ |mℓ| ≤ ℓ
Principal Quantum Number n
■ It results from the solution of R(r) in Eq (7.4) because R(r) includes
the potential energy V(r).
The result for this quantized energy is

■ The negative means the energy E indicates that the electron and
proton are bound together.
 Radial probability density

Radial probability density

r 2 Rnl2 (r )

Orbital n l <r> (au)

1s 1 0 1.5 n2ao

2s 2 0 6.0

2p 2 1 5.0

3s 3 0 13.5

r = ∫ d 3r ψ nlm
*
(r )rψ nlm (r )
∞
2
= ∫ dr r 3 Rnl (r )
0
 Shapes of the spherical harmonics

Y00 Y11 Y10

z
y

x
Re[Y11 ] l = 1, m = 0
l = 0, m = 0
3
1 Y10 = cos θ
Y00 = 4π
4π

l = 1, m = 1
3
Y11 = − sin θ exp(iφ )
8π

(Images from http://odin.math.nau.edu/~jws/dpgraph/Yellm.html)

 Shapes of spherical harmonics (2)

Y22 Y21 Y20

z
y

x Re[Y22 ] Re[Y21 ]
l = 2, m = 0
5
Y20 = (3cos 2 θ − 1)
16π

l = 2, m = 2 l = 2, m = 1
15 15
Y22 = sin 2 θ exp(2iφ ) Y21 = − sin θ cos θ exp(iφ )
32π 8π

(Images from http://odin.math.nau.edu/~jws/dpgraph/Yellm.html)

Orbital Angular Momentum Quantum
Number ℓ
■ It is associated with the R(r) and f(θ) parts of the wave function.

■ Classically, the orbital angular momentum with L =

mvorbitalr.

■ ℓ is related to L by .

■ In an ℓ = 0 state, .

It disagrees with Bohr’s semiclassical “planetary” model of electrons

orbiting a nucleus L = nħ.
Orbital Angular Momentum Quantum
Number ℓ
■ A certain energy level is degenerate with respect to ℓ when the
energy is independent of ℓ.

■ Use letter names for the various ℓ values.

❑ ℓ= 0 1 2 3 4 5...
❑ Letter = s p d f g h...

■ Atomic states are referred to by their n and ℓ.

■ A state with n = 2 and ℓ = 1 is called a 2p state.
■ The boundary conditions require n > ℓ.
 Classical angular momentum
For a classical particle, the angular momentum is
defined by L
L = r×p
p
= Lx i + Ly j + Lz k
r
In components F
Lx = ypz − zp y
Ly = zpx − xpz
Same origin for r and F
Lz = xp y − ypx

Angular momentum is very important in problems dL d dr dp

= (r × p) = × p + r ×
involving a central force (one that is always dt dt dt dt
directed towards or away from a central point) p
because in that case it is conserved = ( × p) + (r × F) = 0.
m
Magnetic Quantum Number mℓ
■ The angle is a measure of the rotation about the z axis.
■ The solution for specifies that mℓ is an integer and related to
the z component of L.

■ The relationship of L, Lz, ℓ, and mℓ

for ℓ = 2.
■ is fixed
because Lz is quantized.
■ Only certain orientations of are
possible and this is called space
quantization.
 The vector model
This is a useful semi-classical model of the quantum results.
Imagine L precesses around the z-axis. Hence the magnitude of L and
the z-component Lz are constant while the x and y components can take a
range of values and average to zero, just like the quantum eigenfunctions.

A given quantum number l determines the z

magnitude of the vector L via

L2 = l (l + 1)!
2

L = l (l + 1)!
L
The z-component can have the 2l+1 values
θ
corresponding to
Lz = m!
, −l ≤ m ≤ l
In the vector model this means that only
particular special angles between the angular
momentum vector and the z-axis are allowed
Magnetic Quantum Number mℓ
■ Quantum mechanics allows to be quantized along only one
direction in space. Because of the relation L2 = Lx2 + Ly2 + Lz2 the
knowledge of a second component would imply a knowledge of the
third component because we know .

■ We expect the average of the angular momentum components

squared to be .
7.4: Magnetic Effects on Atomic Spectra—The
Normal Zeeman Effect
■ The Dutch physicist Pieter Zeeman showed the spectral lines
emitted by atoms in a magnetic field split into multiple energy levels.
It is called the Zeeman effect.
■ A spectral line is split into three lines.
■ Consider the atom to behave like a small magnet.
■ Think of an electron as an orbiting circular current loop of I = dq / dt
around the nucleus.
■ The current loop has a magnetic moment µ = IA and the period T =
2πr / v.
■ where L = mvr is the magnitude of the orbital
angular momentum.
7.4: Magnetic Effects on Atomic Spectra—The
Normal Zeeman Effect

τ = µ x B = dL/dt
The Normal Zeeman Effect

■ Since there is no magnetic field to

align them, point in random
directions. The dipole has a
potential energy

■ The angular momentum is aligned with the magnetic moment, and

the torque between and causes a precession of .

Where µB = eħ / 2m is called a Bohr magneton.

■ cannot align exactly in the z direction and
has only certain allowed quantized orientations.
The Normal Zeeman Effect
■ The potential energy is quantized due to the magnetic quantum
number mℓ.

■ When a magnetic field is applied, the 2p level of atomic hydrogen is

split into three different energy states with energy difference of ΔE =
µBB Δmℓ.

mℓ Energy
1 E0 + µBB
0 E0
−1 E0 − µBB
The Normal Zeeman Effect

■ A transition from 2p to 1s.

The Stern-Gerlach Experiment
■ An atomic beam of particles in the ℓ = 1 state pass through a magnetic
field along the z direction.

■ The mℓ = +1 state will be deflected down, the mℓ = −1 state up, and the
mℓ = 0 state will be undeflected.
■ If the space quantization were due to the magnetic quantum number
mℓ, mℓ states is always odd (2ℓ + 1) and should have produced an odd
number of lines.
7.5: Intrinsic Spin
■ Samuel Goudsmit and George Uhlenbeck in Holland proposed that
the electron must have an intrinsic angular momentum and
therefore a magnetic moment.

■ Paul Ehrenfest showed that the surface of the spinning electron

should be moving faster than the speed of light!

■ In order to explain experimental data, Goudsmit and Uhlenbeck

proposed that the electron must have an intrinsic spin quantum
number s = ½.
Intrinsic Spin
■ The spinning electron reacts similarly to the orbiting electron in a
magnetic field.
■ We should try to find L, Lz, ℓ, and mℓ.
■ The magnetic spin quantum number ms has only two values,
ms = ±½.
The electron’s spin will be either “up” or
“down” and can never be spinning with its
magnetic moment µs exactly along the z axis.

The intrinsic spin angular momentum

vector .
Intrinsic Spin
■ The magnetic moment is .
■ The coefficient of is −2µB as with is a consequence of theory
of relativity.

■ The gyromagnetic ratio (ℓ or s).

■ gℓ = 1 and gs = 2, then

and

■ The z component of .
■ In ℓ = 0 state no splitting due to .

there is space quantization due to the

intrinsic spin.
■ Apply mℓ and the potential energy becomes
7.6: Energy Levels and Electron Probabilities
■ For hydrogen, the energy level depends on the principle quantum
number n.
■ In ground state an atom cannot emit
radiation. It can absorb
electromagnetic radiation, or gain
energy through inelastic
bombardment by particles.
Selection Rules
■ We can use the wave functions to calculate transition probabilities
for the electron to change from one state to another.

Allowed transitions:
■ Electrons absorbing or emitting photons to change states when Δℓ
= ±1.
Forbidden transitions:
■ Other transitions possible but occur with much smaller
probabilities when Δℓ ≠ ±1.
Probability Distribution Functions
■ We must use wave functions to calculate the probability
distributions of the electrons.

■ The “position” of the electron is spread over space and is not

well defined.

■ We may use the radial wave function R(r) to calculate radial

probability distributions of the electron.
■ The probability of finding the electron in a differential volume
element dτ is .
Probability Distribution Functions
■ The differential volume element in spherical polar coordinates is

Therefore,

■ We are only interested in the radial dependence.

■ The radial probability density is P(r) = r2|R(r)|2 and it depends only

on n and l.
Probability Distribution Functions
■ R(r) and P(r) for the
lowest-lying states of
the hydrogen atom.
Probability Distribution Functions
■ The probability density for the hydrogen atom for three different
electron states.