Quantum Theory of the

hydrogen Atom
And
Many-Electron Atoms
 General outline
• Schrödinger Equation in Spherical
coordinates
• The hydrogen atom wave function
• Radial probability densities
• Angular momentum
• Intrinsic spin
• Energy levels
• The Zeeman effect
 The Quantum Model of the
Hydrogen Atom
• The potential energy function for the
hydrogen atom is
e2
U (r ) = − k e
r
– ke is the Coulomb constant
– r is the radial distance from the proton to the
electron
• The proton is situated at r = 0
• The formal procedure to solve the hydrogen
atom is to substitute U(r) into the Schrödinger
equation and find the appropriate solutions to
the equations
• Because it is a three-dimensional problem, it is
easier to solve if the rectangular coordinates
are converted to spherical polar coordinates

h 2  ∂ 2ψ ∂ 2ψ ∂ 2ψ 
−  2 + 2 + 2  + Uψ = Eψ
2m  ∂x ∂y ∂z 
• ψ(x, y, z) is converted to
ψ(r, θ, φ)
• Then, the space variables
can be separated:
ψ(r, θ, φ) = R(r), ƒ(θ), g(φ)
• When the full set of
boundary conditions are
applied, we are led to three
different quantum numbers
for each allowed state
Wave function of the electron in a hydrogen
atom (in spherical polar coordinate)

∂  2 ∂ψ  ∂  ∂ψ  ∂ ψ
2
sin θ  r
2
 + sin θ  sin θ + 2
∂r  ∂r  ∂θ  ∂θ  ∂φ
2

2mr sin θ e
2 2

+  + E ψ = 0
 4πεo r
2
h 
 Quantum Numbers, General
• The three different quantum numbers are
restricted to integer values
• They correspond to three degrees of
freedom
– Three space dimensions
 Principal Quantum Number
• The first quantum number is associated
with the radial function R(r)
– It is called the principal quantum number
– It is symbolized by n
• The potential energy function depends
only on the radial coordinate r
• The energies of the allowed states in
the hydrogen atom are the same En
values found from the Bohr theory
 Orbital and Orbital Magnetic
Quantum Numbers
• The orbital quantum number is symbolized by
ℓ
– It is associated with the orbital angular momentum of
the electron
– It is an integer
• The orbital magnetic quantum number is
symbolized by mℓ
– It is also associated with the angular orbital
momentum of the electron and is an integer
 Quantum Numbers - Summary
of Allowed Values
• The values of n can range from 1 to ∞
• The values of ℓ can range from 0 to n - 1
• The values of mℓ can range from –ℓ to ℓ
• Example:
– If n = 1, then only ℓ = 0 and mℓ = 0 are permitted
– If n = 2, then ℓ = 0 or 1
• If ℓ = 0 then mℓ = 0
• If ℓ = 1 then mℓ may be –1, 0, or 1
Quantum Numbers,
Summary Table
 Shells
• Historically, all states having the same
principle quantum number are said to form
a shell
– Shells are identified by letters K, L, M,…
• All states having the same values of n and
ℓ are said to form a subshell
– The letters s, p, d, f, g, h, .. are used to
designate the subshells for which ℓ = 0, 1, 2,
3,…
Shell and Subshell Notation,
Summary Table
 Wave Functions for Hydrogen
• The simplest wave function for hydrogen is the
one that describes the 1s state and is
designated ψ1s(r)
1
ψ1s (r ) = e −r ao
πao3

• As ψ1s(r) approaches zero, r approaches ∞ and

is normalized as presented
• ψ1s(r) is also spherically symmetric
– This symmetry exists for all s states
 Probability Density
• The probability density for the 1s state is

2  1  −2r ao
ψ1s =  3  e
 πao 
• The radial probability density function P(r) is the
probability per unit radial length of finding the
electron in a spherical shell of radius r and
thickness dr
 Radial Probability Density
• A spherical shell of
radius r and thickness
dr has a volume of
4πr2 dr
• The radial probability
function is P(r) = 4πr2
|ψ|2
P(r) for 1s State of Hydrogen

• The radial probability

density function for the
hydrogen atom in its
ground state is
 4r 2  −2r ao
P1s (r ) =  3  e
 ao 
• The peak indicates the
most probable location
• The peak occurs at the
Bohr radius
 P(r) for 1s State of Hydrogen
• The average value of r for the ground state
of hydrogen is 3/2 ao
– The graph shows asymmetry, with much more
area to the right of the peak
• According to quantum mechanics, the
atom has no sharply defined boundary as
suggested by the Bohr theory
 Electron Clouds
• The charge of the electron
is extended throughout a
diffuse region of space,
commonly called an
electron cloud
• This shows the probability
density as a function of
position in the xy plane
• The darkest area, r = ao,
corresponds to the most
probable region
Wave Function of the 2s state

• The next-simplest wave function for the

hydrogen atom is for the 2s state
– n = 2; ℓ = 0
• The wave function is
3
1  1  2 r  −r 2ao
ψ2 s (r ) =    2 − e
4 2π  ao   ao 

– ψ 2s depends only on r and is spherically symmetric

Comparison of 1s and 2s States
• The plot of the radial
probability density for
the 2s state has two
peaks
• The highest value of
P corresponds to the
most probable value
– In this case, r ≈ 5ao
 Physical Interpretation of ℓ
• The magnitude of the angular momentum
of an electron moving in a circle of radius r
is L = mevr
• The direction of L is perpendicular to the
plane of the circle
• In the Bohr model, the angular momentum
of the electron is restricted to multiples of h
• According to quantum mechanics, an atom in a state
whose principle quantum number is n can take on the
following discrete values of the magnitude of the orbital
angular momentum:
L = l( l + 1 )h l = 0 ,1,2...n − 1
– L can equal zero, which causes great difficulty when attempting
to apply classical mechanics to this system
 Physical Interpretation of mℓ
• The atom possesses an orbital angular
momentum
• There is a sense of rotation of the electron
around the nucleus, so that a magnetic moment
is present due to this angular momentum
• There are distinct directions allowed for the
magnetic moment vector µ with respect to the
magnetic field vector B
• Because the magnetic moment µ of the
atom can be related to the angular
momentum vector, L, the discrete direction
of µ translates into the fact that the
direction of L is quantized
• Therefore, Lz, the projection of L along the
z axis, can have only discrete values
• The orbital magnetic quantum number
mℓ specifies the allowed values of the z
component of orbital angular
momentum
• Lz = mℓ ħ
• The quantization of the possible
orientations of L with respect to an
external magnetic field is often referred
to as space quantization
• L does not point in a specific direction
– Even though its z-component is fixed
– Knowing all the components is inconsistent with
the uncertainty principle
• Imagine that L must lie anywhere on the surface of
a cone that makes an angle θ with the z axis
• L can never be aligned parallel or antiparallel to B
because Lz must be less than the total angular
momentum, L.
• For Lz to be zero, L must be perpendicular to B
• θ is also quantized
• Its values are
specified through
Lz ml
cos θ = =
L l ( l + 1)
• mℓ is never greater
than ℓ, therefore θ can
never be zero
 Zeeman Effect
• The Zeeman effect is the
splitting of spectral lines
in a strong magnetic field
• In this case the upper
level, with ℓ = 1, splits into
three different levels
corresponding to the
three different directions
of µ
• The torque, τ, on a magnetic dipole in the
presence of external magnetic field, B:

τ = µB sin θ
potential energy : θ
θ B
U = ∫ τdθ = −µB cos θ
π/ 2

 e 
µ = − L
 2m 
e
U= LB cos θ
2m
ml  eh 
cos θ = U = ml  B
l (l + 1)  2m 
• µB = eħ/2m = Bohr magneton
= 9.274 x 10-24 J/T
 Spin Quantum Number ms
• Electron spin does not come from the
Schrödinger equation
• Additional quantum states can be
explained by requiring a fourth quantum
number for each state
• This fourth quantum number is the spin
magnetic quantum number ms
• Unusual feature was observed in the
spectra of certain gases, such as sodium
vapor
• Close examination shows that one
prominent line in the spectra is actually
consist of 2 closely spaced lines (doublet)
– Fine Structure
• A need for a new quantum number!
Stern–Gerlach experiment
• If the particle travels through an
inhomogeneous magnetic field, then the force
on one end of the dipole will be slightly
greater than the opposing force on the other
end of the dipole.
• This leads to the particle being deflected in
the inhomogeneous magnetic field. The
direction in which the particles are deflected
is typically called the "z" direction.
• If the particles are classical, "spinning" particles,
then the distribution of their spin angular momentum
vectors is taken to be truly random and each particle
would be deflected up or down by a different amount,
producing an even distribution on the screen of a
detector.
• Instead, the particles passing through the device are
deflected either up or down by a specific amount.
This can only mean that spin angular momentum is
quantized, i.e. it can only take on discrete values.
There is not a continuous distribution of possible
angular momenta.
 Electron Spins

• Only two directions exist for

electron spins
• The electron can have spin
up (a) or spin down (b)
• In the presence of a
magnetic field, the energy
of the electron is slightly
different for the two spin
directions and this
produces doublets in
spectra of certain gases
• The concept of a spinning electron is
conceptually useful
• The electron is a point particle, without any
spatial extent
– Therefore the electron cannot be considered to be
actually spinning
• The experimental evidence supports the
electron having some intrinsic angular
momentum that can be described by ms
• Dirac showed this results from the relativistic
properties of the electron
 Spin Angular Momentum
• The total angular momentum of a particular
electron state contains both an orbital
contribution L and a spin contribution S
• Electron spin can be described by a single
quantum number s, whose value can only be s =
½
• The spin angular momentum of the electron
never changes
• The magnitude of the spin angular momentum is
3
S = s(s + 1)h = h
2
• The spin angular momentum can have two
orientations relative to a z axis, specified by the
spin quantum number ms = ± ½
– ms = + ½ corresponds to the spin up case
– ms = - ½ corresponds to the spin down case
• The z component of
spin angular
momentum is Sz =
ms ħ = ± ½ ħ
• Spin angular
moment S is
quantized
 Spin Magnetic Moment
• The spin magnetic moment µspin is related
to the spin angular momentum by
e
µspin =− S
me
• The z component of the spin magnetic
moment can have values
eh
µspin , z =±
2me
 The Exclusion Principle
• The four quantum numbers discussed so far can
be used to describe all the electronic states of
an atom regardless of the number of electrons in
its structure
• How many electron can be in a particular
quantum state?
• The exclusion principle states that no two
electrons can ever be in the same quantum state
– Therefore, no two electrons in the same atom can
have the same set of quantum numbers
 Filling Subshells
• Once a subshell is filled, the next electron
goes into the lowest-energy vacant state
– If the atom were not in the lowest-energy
state available to it, it would radiate energy
until it reached this state
 Orbitals
• An orbital is defined as the atomic state
characterized by the quantum numbers n,
ℓ and mℓ
• From the exclusion principle, it can be
seen that only two electrons can be
present in any orbital
– One electron will have spin up and one spin
down
 Allowed Quantum States,
Example

• In general, each shell can accommodate up

to 2n2 electrons
 Hund’s Rule
• Hund’s Rule states that when an atom has
orbitals of equal energy, the order in which
they are filled by electrons is such that a
maximum number of electrons have
unpaired spins
– Some exceptions to the rule occur in
elements having subshells that are close to
being filled or half-filled
 Periodic Table
• The chemical behavior of an element
depends on the outermost shell that
contains electrons
• For example, the inert gases (last column)
have filled subshells and a wide energy
gap occurs between the filled shell and the
next available shell
 Hydrogen Energy Level
Diagram Revisited
• The allowed values of ℓ
are separated
• Transitions in which ℓ
does not change are
very unlikely to occur
and are called forbidden
transitions
– Such transitions actually
can occur, but their
probability is very low
compared to allowed
transitions
 Selection Rules
• The selection rules for allowed transitions are
– ∆ℓ = ±1
– ∆mℓ = 0, ±1
• The angular momentum of the atom-photon
system must be conserved
• Therefore, the photon involved in the process
must carry angular momentum
– The photon has angular momentum equivalent to that
of a particle with spin 1
– A photon has energy, linear momentum and angular
momentum
 Multielectron Atoms
• For multielectron atoms, the positive nuclear
charge Ze is largely shielded by the negative
charge of the inner shell electrons
– The outer electrons interact with a net charge that is
smaller than the nuclear charge
• Allowed energies are

2
13.6 Zeff
En = − 2
eV
n
Z eff2 = effective atomic number