Focus 8: The Structure of

Atoms
 Topic 8A: Hydrogenic Atoms
• Hydrogenic atom is a one-electron atom or
ion of atomic number Z.
Examples: He+, Li2+, C5+, O7+ , U91+
(Schrödinger eqn. can be solved exactly)
Concepts from these solutions can be
used to describe many-electron atoms or
ions.
Many-electron species is an atom or ion
with more than one electron.
 The spectrum of atomic
hydrogen
• ∆𝐸 = ℎ𝑐𝜈 (Bohr frequency condition)
𝟏 𝟏
 Rydberg Equation: 𝝂 = 𝑹𝑯 −
𝒏𝟏 𝟐 𝒏𝟐 𝟐
where n1= 1, 2….., n2 = n1 + 1, n1 + 2,…….

RH= 109677 cm-1

 Potential Energy of an electron
in a hydrogenic atom
• Background: Rutherford’s nuclear model
 Schrödinger equation will have potential
energy term, V(r): Coulombic interaction
between nucleus of charge +Ze and the
electron of charge e.
𝑍𝑒 2
𝑉 𝑟 = − | ε0 is the vacuum permittivity.
4𝜋𝜀𝑜 𝑟
 V(r) becomes more negative as the distance
between the nucleus and electron decreases.
 Energy Levels of a Hydrogenic Atom
𝒉𝒄𝑹𝑵 𝒁𝟐
• 𝑬𝒏 = −
𝒏𝟐
| Allowed energy levels of a hydrogenic atom.
𝜇𝑒 4 𝑚𝑒 𝑚𝑛
• 𝑅𝑁 = 𝑤ℎ𝑒𝑟𝑒 𝜇 =
8𝜀𝑜 2 ℎ3 𝑐 𝑚𝑒 +𝑚𝑛
| Rydberg constant and reduced mass.
 Significance of Z2:
 1. Z times the greater strength of nuclear field.
 2. Electron is Z times more likely to be found
closer to the nucleus.
 Discrete Energy Levels of
Electron in Hydrogen Atom
 At low values of
principal quantum
number n, the energy
levels are widely
separated.
 At high values of n, the
electron energy levels
are closely spaced.
 The ground state of the
hydrogen atom has
n=1
 Emission from discrete electronic
energy levels in hydrogen atom
𝒉𝒄𝑹𝑯 𝒉𝒄𝑹𝑯
• 𝜟𝑬 = − 𝟐 − − 𝟐
𝒏𝟐 𝒏𝟏
 This energy is carried away by a photon of
energy hc𝜈.
 n1 and n2 are principal quantum numbers.
 Example Problem: The shortest wavelength
transition in Paschen series in hydrogen
occurs at 821 nm. What will be the
wavelength of the same transition in Li2+?
 Ionization Energy
• The minimum energy needed to
completely remove an electron from an
atom is called Ionization Energy (I).
• 𝑰 = 𝒉𝒄𝑹𝑯 𝒁𝟐 | Ionization energy scales as
directly proportional to Z2.
• Example Problem: What is the ionization
enegy of a He+ hydrogenic atom (in eV)?
Hydrogenic Atoms: Spherical polar
coordinates for orbitals
Hydrogenic orbitals:
Spherical polar coordinate
appropriately describes the
motion of electrons
around the equator and
Q poles as the Wavefunction of
a given orbital
repeats itself around the
equator and poles
𝒙 = 𝒓𝒔𝒊𝒏𝜽𝒄𝒐𝒔𝝓, 𝒚 = 𝒓𝒔𝒊𝒏𝜽𝒔𝒊𝒏𝝓, 𝒛 = 𝒓𝒄𝒐𝒔𝜽
 Quantum Numbers
• Hydrogenic Orbital
𝝍𝒏,𝒍,𝒎𝒍 𝒓, 𝜽, 𝝓 = 𝑹𝒏,𝒍 (𝒓) × 𝒀𝒍,𝒎𝒍 (𝜽, 𝝓)
𝑹𝒏,𝒍 𝒓 - Radial Wave function
𝒀𝒍,𝒎𝒍 (𝜽, 𝝓)-Angular Wavefunction
Quantum Number Name Allowed Determines
values
n Principal 1, 2, ….. En = -hcRN Z2
/ n2
l Orbital angular 0, 1, …., n-1 J = [l(l+1)]1/2 ℏ
momentum
ml Magnetic 0, ±1,…..,±l Z-Component of
orbital angular
momentum . Jz = mlℏ
Concept of l and ml : spherical surface
representation of angular part
• A representation of the wavefunctions of a
particle as spherical harmonics
 Orbital and magnetic quantum
numbers: Vector representation Example for
l=2
• Magnitude Orbital angular momentum in
terms of ℏ: 6ℏ
Radial and Angular Wavefunctions
(Table 8A.1)
Hydrogenic atom total wavefunctions:
Some Examples
• 𝜓1𝑠 = 𝑹𝒏,𝒍 𝒓 × 𝒀𝒍,𝒎𝒍 𝜽, 𝝓
3 2 𝑍𝑟
𝑍 − 1
= 2× × 𝑒 𝑎𝑜 ×
𝑎𝑜 2𝜋1 2
1 2 𝑍𝑟
𝑧3 −
= × 𝑒 𝑎𝑜
𝜋𝑎𝑜3
• 𝜓2𝑠
3 2 𝑍𝑟
1 𝑍 𝑍𝑟 −
2𝑎
1
= 1 2× × 2− ×𝑒 𝑜 ×
8 𝑎𝑜 𝑎𝑜 2𝜋 1 2
Radial Wavefunctions: Examples

1s 2p

2s 3p

3s 3d
 Quantum Numbers: Hydrogenic
Atoms
• For Hydrogenic atoms:
 The energy depends only on the principal quantum number, n.
 All orbitals of the same value of n but different values of l and ml
have the same energy- degenerate wavefunction.
Mean radius or distance:
𝒏𝟐 𝒂𝒐 𝟏 𝒍(𝒍+𝟏)
 𝒓 𝒏,𝒍,𝒎𝒍 = 𝟏+ 𝟏−
𝒁 𝟐 𝒏𝟐

ao = 52.9177 pm (Bohr radius)

• The average distance from the nucleus increases as n2.

• For a given n, l, the mean distance decreases with increasing Z.

Orbital degeneracy of the Hydrogenic
atom
• Orbital degeneracy of hydrogenic atom is
n2. Subshells (l)
l=0 l=1 l=2
0 3s -1 0 +1 3p -2 -1 0 +1 +2 3d M shell,
n=3
2s 2p
shells (n)

0 -1 0 +1 L shell, n = 2

1s Example Problem:
0 K shell, n = 1
What is the
degeneracy of an
Orbital with n = 5?
 The 1s orbital: Wavefunction and
Probability
1/2 𝑟
1 − 1
• 𝜓1𝑠,𝐻 = 2 × ×𝑒 𝑎𝑜 × = R1,0 × Y0,0
𝑎𝑜 3 2𝜋1/2
𝟏/𝟐 𝒓
𝟏 −
𝒆 𝒂𝒐
𝝅𝒂𝟑𝒐
(Normalized wavefunction)
4𝜋𝜀𝑜 ℏ2
 𝑎𝑜 = # Definition of the Bohr radius
𝑚𝑒 𝑒 2
 Probability of finding an electron in a small volume
δV at a given point is equal to Ψ2δV
1
 The angular wavefunction, Y0,0 =
2𝜋1/2
 The 1s orbital: Wavefunction and
Total energy
The balance of kinetic
and potential energies
in the ground state H.
 The 1s orbital: Wavefunction and
Probability density
• Ψ -Wavefunction, Ψ2 –Probability density
 Spherically symmetric s orbitals and
boundary surface of s orbital
• Representations of first 2 hydrogenic s
orbitals
 Probability using normalized orbital
wavefunction of Hydrogen
• Example Problem: Calculate the
probability of finding a 1s electron in a small
volume of 1 pm3 centred on the
H-atom. At nucleus => r = 0 =>
and using normalized wavefunction for 1s
𝑃𝑟𝑜𝑏𝑎𝑏𝑖𝑙𝑖𝑡𝑦 = 𝜓 2 𝛿𝑉
𝟏 𝟏 𝟑
𝟑 × 𝜹𝑽 = 𝟑
× 𝟏. 𝟎𝒑𝒎 =?
𝝅𝒂𝒐 𝝅 × (𝟓𝟐. 𝟗𝒑𝒎)
 Radial Distribution Function
• 𝑃𝑟𝑜𝑏𝑎𝑏𝑖𝑙𝑖𝑡𝑦 = 𝑃 𝑟 𝛿𝑟
 𝑃 𝑟 = 4𝜋𝑟 2 𝜓 2
| radial distribution function
for s orbitals or spherically
symmetric distribution.
 General form of the radial distribution
function:
𝑃 𝑟 = 𝑟 2 𝑅(𝑟)2
| R(r) is the radial wavefunction.
 Radial Distribution Function in s
orbital
• Step 1: Calculate the volume of the
spherical shell.
• Step 2: Use Born interpretation to write an
expression for the probability.
• Step 3: Apply the result to an s orbital.
 r2 increases from 0 as r increases, Ψ2
decreases towards 0.
 P(r) goes through maximum and declines
to 0
 Radial Distribution Function
• Radial distribution function (R(r))gives the
probability that the electron will be found
anywhere in a shell of radius r and
thickness δr.
 Concept of most probable radius of
hydrogenic atom in 1s orbital
1 2 𝑍𝑟
𝑍3 −𝑎
• 𝜓1𝑠 = ×𝑒 𝑜
𝜋𝑎𝑜3
2𝑍𝑟
𝑍3 −
• 𝑃 𝑟 𝛿𝑟 = 4𝜋𝑟 2 𝜓 2 𝛿𝑟, 𝑃 𝑟 = 4𝜋𝑟 2 × ×𝑒 𝑎𝑜
𝜋𝑎𝑜3
2𝑍𝑟
𝑑𝑃 4𝑍 3 2𝑍𝑟 2 −𝑎
• = 2𝑟 − ×𝑒 𝑜
𝑑𝑟 𝑎𝑜3 𝑎𝑜
2𝑍𝑟
8𝑟𝑍 3 𝑍𝑟 −𝑎 𝑍𝑟
= 1 − ×𝑒 𝑜 = 0 => 1 − =0
𝑎𝑜3 𝑎𝑜 𝑎𝑜
Most probable radius: At maximum of probability distribution
curve r = rmp
𝑎𝑜
𝑟𝑚𝑝 = | for hydrogenic atom
𝑍
Radial Distribution Function: Example
• Example Problem: Consider an electron in 1s
orbital of a hydrogen atom. Calculate the
probability that electron will be found
anywhere in a shell formed by a sphere of
radius ao and a sphere of radius 1 pm higher.
(Assume that wavefunction is constant within
this spherical shell) δr

 Probability:
𝑃 𝑟 𝛿𝑟 = 𝑃 𝑟 𝛿𝑟 @𝑟 = 𝑎𝑜 a
o

= 4𝜋𝑟 2 𝜓 2 𝛿𝑟 = ?
 Probability of finding an electron:
Some problem types
 Calculation of probability in a small volume (δV ~ 1
pm3) where wavefunction is constant.
E. g. , 1s orbital of H − atom
2
𝑃𝑟𝑜𝑏𝑎𝑏𝑖𝑙𝑖𝑡𝑦 = 𝜓1𝑠,𝐻 × 𝛿𝑉
2𝑟
1 −𝑎
= ×𝑒 𝑜 × 1𝑝𝑚3
𝜋𝑎𝑜3
where probability at a distance r from the nucleus in a
small volume of interest can be calculated.
[Note: If wavefunction is not constant, integration of 𝜓 2
within the limits of region of space of interest is
required.]
 Probability of finding an electron:
Some problem types
 Calculation of probability that the electron will be found anywhere
between a shell of radius a0 and a shell of radius 1 pm higher,
considering wave function is constant in the spherical shell.
(e.g,1s orbital of H-atom).

𝑃𝑟𝑜𝑏𝑎𝑏𝑖𝑙𝑖𝑡𝑦 = 𝑃 𝑟 𝛿𝑟 = 4𝜋𝑟 2 𝜓 2 𝛿𝑟
2𝑟
1 −𝑎
= 4𝜋𝑟 2 × ×𝑒 𝑜 × 1𝑝𝑚
𝜋𝑎𝑜3

Note: 1. If wavefunction is not constant, integration of 𝜓 2

within the limits of region of space of interest is required.
2. In general, for an orbital of nonspherical symmetry
𝑟 2 𝑅(𝑟) 2 is to be used as radial distribution function.
 Radial Wavefunctions: Examples
• Example radial Wavefunctions: 1s, 2s, 3s,
2p, 3p, 3d
 Radial Wavefunctions: Nodes
• Number of radial nodes = n-l-1
 Example Problems: 1. How many radial
nodes are there in a 4s orbital?
2. Refer Table 8A.1: Locate the radial node
of 2s orbital of hydrogenic atom
𝑍𝑟
1 𝑍 3/2 𝑍𝑟 −
𝑅 𝑟 2𝑠 = 2 − 𝑒 2𝑎𝑜
81/2 𝑎𝑜 𝑎𝑜
2𝑎𝑜
Radial node is at a point where: 𝑟 =
𝑍
 Angular Part of Wavefunction
• Refer Table 8A.1: Angular part of the
wavefunction is constant for an s orbital
(spherically symmetric).
Example Problem: for locating angular
node in H-atom:
1/2 𝑟
1 −
2𝑎𝑜
𝜓 2𝑝𝑧 = × 𝑟𝑐𝑜𝑠𝜃 × 𝑒
32𝜋𝑎𝑜5
𝜋
Angular node is at 𝜃 =
2
 The boundary surfaces of p orbitals

• p orbitals have n-2 radial nodes.

• Magnitude of angular momentum of p
electron = 2 ℏ
 The boundary surfaces of d orbitals
• d orbitals have n-3 radial nodes.
 Topic 8B: Many-electron atoms
• The orbital approximation:
The wavefunction of several non-interacting
particles is the product of wavefunctions for each
particle.
𝜓 1,2 … = 𝜓 1 𝜓 2 … …
• Many-electron wavefunctions: Consider two-
electron system:
{𝐻 (1) + 𝐻 (2)+𝜓(1,2) = 𝐸𝜓(1,2)
{𝐻 (1) + 𝐻 (2)+ 𝜓 1 𝜓 2 =*𝐸 1 + 𝐸(2)+ 𝜓 1,2
 Orbital Approximation: Example
• He atom: 1s2
Overall Wavefunction of two electrons in 1s orbital of
He atom through orbital approximation
𝜓 1,2 = 𝜓 1 𝜓 2
1 2 2𝑟1 1 2 2𝑟
8 − 8 − 2
= × 𝑒 𝑎𝑜 × × 𝑒 𝑎𝑜
𝜋𝑎𝑜3 𝜋𝑎𝑜3
8 2(𝑟 +𝑟 )
− 1 2
= × 𝑒 𝑎𝑜
𝜋𝑎𝑜3
 Electron Spin
• Electron spin is described by spin
quantum number, ms= ½
• The spin can be clockwise or
anticlockwise.
• The two states are distinguished by the
spin magnetic quantum number
1 1
+ 𝑜𝑟 −
2 2

CLASSICAL PICTURE OF SPIN

Electron Spin: Experimental evidence

• Otto Stern and Walther Gerlach (1921-22):

 A beam of silver (Ag) atoms was directed
through a strong, inhomogeneous magnetic
field.
 Silver atom has 47 electrons. There are 23 ↑ up
and 23 ↓ down spins.
 The remaining 1 electron will be influenced by
the magnetic field and deviate as per two spin
states of a single electron.
Electron Spin: Experimental evidence

CLASSICALLY EXPECTED

QUANTIZATION OBSERVED

𝑻𝒉𝒆 𝒎𝒂𝒈𝒏𝒊𝒕𝒖𝒅𝒆 𝒐𝒇 𝒕𝒉𝒆 𝒔𝒑𝒊𝒏 𝒂𝒏𝒈𝒖𝒍𝒂𝒓

𝒎𝒐𝒎𝒆𝒏𝒕𝒖𝒎 𝒐𝒇 𝟏 𝒆𝒍𝒆𝒄𝒕𝒓𝒐𝒏 =
𝟑
×ℏ
𝟐
 Fundamental particles:
spin ½ and spin 1 particles
• Fundamental Particles:
Spin ½ Particles
• Electrons (filling in orbitals follow Pauli
exclusion principle),
Protons, Neutrons (fermions)
Spin 1 particles
• Photons (bosons)
 Matter consists of fermions bound together
by exchange of bosons
 Penetration and Shielding
 An electron at a distance r from
the nucleus experiences a coulombic
repulsion from all electrons within
a sphere of radius r and which is
equivalent to point negative charge
on the nucleus.
 An electron in an s orbital
orbital is more likely to be
found
close to the nucleus
than an
electron in p orbital
The occupation of d orbitals

 Strong electron-
4s electron repulsions in
3d orbitals are
minimized in the
ground state of a
3d scandium atom if
atom has the
configuration
[Ar]3d14s2
 8C: Periodic trends of atomic
properties
• The variation Effective nuclear charge versus
Atomic number
 Periodic trends of atomic properties
• Atomic radius versus atomic number:
 Periodic trends of atomic properties

• Ionization energy versus Atomic number

 8D.1 Atomic Spectroscopy
• Relevant Eqns.:
1. 𝒉𝒄𝑹𝑵 𝒁𝟐
𝑬𝒏 = − 𝟐
𝒏
2. ∆𝑬 = 𝒉𝒄𝝂
• Selection rule: Independent of n, total
angular momentum of the atom and
photon are conserved during the
transition.
∆𝒍 = ±𝟏, ∆𝒎𝒍 = 𝟎, ±𝟏
 Grotrian Diagram for Atomic
Hydrogen Spectrum
• Energies of states and allowed transitions:
 Grotrian Diagram for Atomic
Hydrogen Spectrum
• Example Question: In the Balmer series of H-
atom spectra, the H𝛿 line has a wavenumber of
24380 cm-1. Identify the principal quantum
number of the level from which the transition
takes place. (report your answer to nearest
integer)
𝟏 𝟏
Eqn. to use: Rydberg Equation: 𝝂 = 𝑹𝑯 −
𝒏𝟏 𝟐 𝒏𝟐 𝟐
Summary of Equations
 Additional Resources

 http://www.rsc.org/periodic-table

(For self study portion periodic properties of elements)