-Atomic Systems (Topic 3)

3.1. Hydrogenic Atoms

Outline
1. Atomic Spectrum of Hydrogen
2. Solving Schrödinger Equation of
hydrogenic atoms
3. Atomic orbitals and Energies
4. Shells and subshells
 Shells and Sub-shells
Shell (characterized by principal quantum number n)
It is common to refer to successive shells by letters:

Sub-Shell (characterized by orbital angular momentum quantum number l)

These subshells are also generally referred to by letters:
 Shells and Sub-shells
Shell (characterized by principal quantum number n)
It is common to refer to successive shells by letters:

Sub-Shell (characterized by orbital angular momentum quantum number l)

These subshells are also generally referred to by letters:

In a hydrogenic atom (and only in a hydrogenic

atom), all orbitals of given n in the same shell
have the same energy. The number of orbitals
in a shell of principal quantum number n is n2,
so in a hydrogenic atom each energy level is
n2-fold degenerate.

All orbitals of the same subshell have the same

energy in all kinds of atoms, not only
hydrogenic atoms.
 Shells and Sub-shells
Shell (characterized by principal quantum number n)
It is common to refer to successive shells by letters:

Sub-Shell (characterized by orbital angular momentum quantum number l)

These subshells are also generally referred to by letters:

When n = 1 there is only one subshell with l =

0, and that subshell contains only one orbital
with ml = 0 (the only value of ml permitted).
When n = 2, there are four orbitals, one in the
s subshell with l = 0 and ml = 0, and three in
the l = 1 sub-shell with ml = +1, 0, −1.
When n = 3 there are nine orbitals (one with l
= 0, three with l = 1, and five with l = 2).
 The Ground State of the Hydrogen Atom
Ground state, the state of lowest energy
When n = 1, the only possible values of other
quantum numbers are l = 0 and ml = 0.

The energy levels of a hydrogen atom.

Old slide
Solving Schrödinger Equation for Hydrogenic Atoms
3. Solving the electronic angular wavefunctions
2
Λ Yl,ml (θ , ϕ ) = −l(l +1)Yl,ml (θ , ϕ )
Schrödinger equation for a particle free to move at constant
radius around a central point:
The allowed solutions are the spherical harmonics specified
by the quantum numbers l and ml.

Spherical harmonics for Schrodinger equation

https://www.youtube.com/watch?v=yRJ2Xf2oH5w&list=PLWt5FuzgdX4nsEeVG4nBdpD
AtIYFq20OG&index=7
Old slide
Solving Schrödinger Equation for Hydrogenic Atoms
5. Solving the electronic radial wavefunctions
 The Ground State of the Hydrogen Atom
Ground state, the state of lowest energy
when n = 1, the only possible values of other
quantum numbers are l = 0 and ml = 0.

= .

The energy levels of a hydrogen atom. For hydrogen atom, Z = 1,

This wavefunction is independent of angle and has

the same value at all points of constant radius; the 1s
orbital (the s orbital with n = 1, and in general ns) is
‘spherically symmetrical’.

The wavefunction decays exponentially from a

maximum value of at the nucleus (at r = 0).
 1s orbital
Physical understanding of the ground state wavefunction:
Potential energy: lower closer to nucleus
Two competing factors (more negative)

Kinetic energy: higher closer to nucleus

E = <Ek> + <V> (higher average curvature)

(higher average curvature)

l=0
Coulombic term:
Attractive force on electron at all radii

(more negative V)

The actual ground-state wavefunction is a compromise between these two extremes:

The wavefunction spreads away from the nucleus (so the expectation value of the
potential energy is not very low nor very high) and has a reasonably low average
curvature (so the expectation of the kinetic energy is not very low nor very high).
 1s orbital
The orbitals
with l = 0
have a non-
zero and
finite value

at the
nucleus
One way of depicting the probability density
(r = 0).
of the electron is to represent |ψ|2 by the
density of shading.
The probability density of the electron is
greatest at the nucleus (r = 0).
Boundary surface mirrors the shape of the
orbital and captures a high proportion (typically
about 90 %) of the electron probability.

For the 1s orbital, the

boundary surface is a
sphere centred on the
nucleus.
 ns orbital
Radial nodes: a small volume element with zero probability of
finding the electron.
All s orbitals are spherically symmetric, but differ in the number
of radial nodes. In general, an ns orbital has n − 1 radial nodes.
As n increases, the radius of the spherical boundary surface that
captures a given fraction of the probability also increases.

For example:
The 1s, 2s, and 3s orbitals
have 0, 1, and 2 radial
nodes, respectively.

Where is the radial node

of a 2s orbital?
Old slide
Solving Schrödinger Equation for Hydrogenic Atoms
5. Solving the electronic radial wavefunctions
 ns orbital
Radial nodes: a small volume element with zero probability of
finding the electron.
All s orbitals are spherically symmetric, but differ in the number
of radial nodes. In general, an ns orbital has n − 1 radial nodes.
As n increases, the radius of the spherical boundary surface that
captures a given fraction of the probability also increases.
2s orbital:
R2,0 ∝ (2 − ρ )
The radial node is found at
(associated Laguerre polynomial factor = 0)
ρ=2

For hydrogen atom,

Z = 1,
na0 ρ
r= = 2a0
2
Radial Distribution Functions
|ψ|2 is a probability density
(dimensions: 1/volume)
|ψ|2 dτ is a (dimensionless) probability 1

Use a detector with a fixed volume dτ to move

around near the nucleus of a hydrogenic atom.

This detector (the small cube) gives

greatest reading at the nucleus. The
reading from the detector decreases
exponentially as the probe is moved
out along any radius.
The reading from the detector is
constant if the probe is moved
on a circle of constant radius at
any orientation: the s orbital is
spherically symmetrical.
Radial Distribution Functions
|ψ|2 is a probability density
(dimensions: 1/volume)
|ψ|2 dτ is a (dimensionless) probability 1

Consider the total probability of finding the

electron anywhere between the two surfaces
of a spherical shell of thickness dr at radius r.
The detection volume is now the
volume of the shell, 4πr2dr
4πr2dr (surface area, 4πr2 × thickness, dr).
This detection volume is zero at the
nucleus (r = 0) and increases with
distance from the nucleus (r > 0).
The probability that the electron will
be found between the inner and outer
surfaces of this shell is |ψ(r)|2 4πr2dr.
Radial Distribution Functions
|ψ|2 is a probability density
(dimensions: 1/volume) dτ
|ψ|2 dτ is a (dimensionless) probability
|ψ(r)|2 4πr2dr
volume of the shell at radius r, 4πr2dr
(surface area, 4πr2 × thickness, dr)

4πr2dr

But, what if there are orbitals that are not

spherically symmetrical?
 Radial Distribution Functions
Deriving the general form of the radial distribution function

R (radial wavefunciton): Y (angular wavefunciton):

electrons move between electrons move around the
concentric surfaces. nucleus on a spherical surface.

|ψ|2 dτ is a (dimensionless) probability

dτ = dxdydz
|RY|2dτ is the probability of finding an electron in a volume element dτ

dτ = dxdydz dτ = r2 sinθ drdθdΦ

 Radial Distribution Functions
Deriving the general form of the radial distribution function

R (radial wavefunciton): Y (angular wavefunciton):

electrons move between electrons move around the
concentric surfaces. nucleus on a spherical surface.

|ψ|2 dτ is a (dimensionless) probability

dτ = dxdydz
|RY|2dτ is the probability of finding an electron in a volume element dτ

dτ = r2 sinθ drdθdΦ
 Radial Distribution Functions
Deriving the general form of the radial distribution function

R (radial wavefunciton): Y (angular wavefunciton):

electrons move between electrons move around the
concentric surfaces. nucleus on a spherical surface.

|ψ|2 dτ is a (dimensionless) probability

dτ = dxdydz
|RY|2dτ is the probability of finding an electron in a volume element dτ

0≤θ≤π
0 ≤ φ ≤ 2π dτ = r2 sinθ drdθdΦ

The angular part of the wavefunction is normalized as

 Radial Distribution Functions
Deriving the general form of the radial distribution function

R (radial wavefunciton): Y (angular wavefunciton):

electrons move between electrons move around the
concentric surfaces. nucleus on a spherical surface.

|ψ|2 dτ is a (dimensionless) probability dτ = dxdydz

|RY|2dτ is the probability of finding an electron in a volume element dτ
|R|2|Y|2dτ
|R|2|Y|2 r2 sinθ drdθdΦ
|R|2|Y|2 r2 dr sinθ dθdΦ dτ = r2 sinθ drdθdΦ
R(r)2|Yl,ml|2 r2 dr sinθ dθdΦ
 Radial Distribution Functions
|ψ|2 is a probability density
(dimensions: 1/volume)
|ψ|2 dτ is a (dimensionless) probability 1

Radial distribution function is a probability density

is the probability of finding
the electron anywhere between the two walls of a
spherical shell of thickness dr at the radius r.
For a 1s orbital, R(r) = a = a0
3 3
2
=r [ 2
] =r 2 4 3 =r 2 4 3
0
(2Z/na0)r
 Radial Distribution Functions
For a 1s orbital,

Physical interpretation:
• Because r2 = 0 at the nucleus, P(0) = 0. The volume of
the shell is zero when r = 0 so the probability of finding
the electron in the shell is zero.
• As r → ∞, P(r) → 0 on account of the exponential term. The wavefunction has
fallen to zero at great distances from the nucleus and there is little probability of
finding the electron even in a large shell.

• The increase in r2 and the decrease in

the exponential factor means that P
passes through a maximum at an
intermediate radius; it marks the
most probable radius at which the
electron will be found regardless of
direction.