Chem-1020: General Chemistry I(B)

Chapter 2*: Atomic Structure and Periodicity

Key Words:
 Quantum Mechanical Model of Atomic Structure (the 5th model)
 Periodicity

Questions to be addressed: What are the key concepts in the quantum mechanical model
(or the modern view and the 5th model) of atomic structure and
how does it account for the periodicity?

*Kind Reminding: Chapter-2 is one of the KEY chapters of Chem-1020, and has also been
claimed to be THE MOST difficult chapter to comprehend in Chem-1020!
Please seek help when in need!

Prof. Xiao-Yuan Li, Dept. of Chemistry, HKUST

Chem-1020: General Chemistry I(B)
Chapter 2*: Atomic Structure and Periodicity
(* One of the KEY chapters of Chem-1020.)
 Key Concepts:
1. Where and how did Bohr’s atomic model (the 4th model) fail?
2. Quantum mechanical model of atomic structure (and its limitations);
3. Atomic orbitals and their representation by quantum numbers and/or by graphs;
4. Electron spin and Pauli principle;
5. Electronic structure in multi-e atoms (precaution!);
6. Periodic table of the elements and quantum mechanical model of atomic structure.

 Reading Assignment: Z&Z: Chapter 2: pp. 52 ~ 97.

 Questions/Exercises Assignment: Z&Z, Chapter 2: pp. 97 ~ 99; 99a ~ 99j.
 For Review: pp. 97 ~ 98.
 Review Questions: 1 to 10.
 Questions: 19, 21, 23, 25, 27, 29, 35, 37.
 Exercises: 39, 41, 43, 45, 47, 49, 51, 53, 55; 57, 59, 61, 63, 65, 67; 69, 71, 73,75;
77, 79, 81, 83, 85; 87, 89, 91, 93, 95, 97, 99, 101,103, 105; 107, 109, 111, 113,
115, 117, 119, 121, 123, 125, 127; 129, 131, 133.

Prof. Xiao-Yuan Li, Dept. of Chemistry, HKUST

Chapter 2: Atomic Structure and Periodicity

OUTLINE :
2.1 The Bohr model of atomic structure: shell-like “orbits” and its merits and failures
2.2 Quantum mechanical model of atomic structure: atomic orbitals (AOs)
2.3 Atomic orbitals: quantum numbers
2.4 Atomic orbitals: shapes(graphs) and relative energies
2.5 Electron’s non-orbital motion: spin and the Pauli principle
2.6 Multi-electron atoms: Be (very) cautious about the concept of atomic orbitals
2.7 The periodic table of elements and the Aufbau principle
2.8 Period trends in atomic properties
2.9 The properties of two selected groups
2.10 Key concepts checklist

Prof. Xiao-Yuan Li, Dept. of Chemistry, HKUST

Section 2.1: The Bohr model of atomic structure: shell-like “orbits”

The main objective of this section is to discuss the Bohr model (4th model)
for atomic structure in more detail, and to see in what aspects it is
conceptually important and quantitatively successful and in what aspects it
completely failed, and therefore a newer model for atomic structure is
called for.

 The Bohr Model for atomic structure: its main points.

 The Bohr Model: the quantitative aspect only works for one e-atom(e.g., H, He+)
 The Bohr Model: its successes and failures

Prof. Xiao-Yuan Li, Dept. of Chemistry, HKUST

 Section 2.1: The Bohr model of atomic structure: shell-like “orbits”

Bohr Model (1913, the 4th Model):

 It was built on the basis of Rutherford’s nuclear model plus a key
experimental observation not explainable by Rutherford model:
 Discrete lines in the absorption/emission spectra of H atoms.

X  Atom consists of a small positively charged nucleus surrounded by

electrons that travel in circular orbits around the nucleus, similar
in structure to the solar (planetary) system.

  The energies of these orbits can only adopt certain fixed values (quantized). Niels Bohr
(1885 –1962, Danish)


Nobel Prize in Phys 1922
 Emitted (or absorbed) light correspond to the energy released
(or absorbed) when electron jumps from one orbit to another orbit,
therefore, to the energy difference between two orbits.

 The larger the value n (integer), the larger the orbit radius;
+
 The larger the value n, the higher the orbit energy;
 Absorption of light: electron jumps from smaller n  larger n;
 Emission of light: electron jumps from larger n  smaller n;

Prof. Xiao-Yuan Li, Dept. of Chemistry, HKUST

Section 2.1: The Bohr model of atomic structure: shell-like “orbits”

Bohr Model: quantitative aspect for H (or H-like) atom only

Energy Level Diagram Orbit-Transition Diagram H line spectrum

Energy levels available to the electron in the H atom : Energy in H line spectrum :
𝟐
𝒁
 En = -2.178 x 10-18 J ( ), ( where Z = 1 for H )  Ephoton = Enf – Eni = DE =
𝒏𝟐 𝟐 𝟏 𝟏
𝟐 –
𝒁 = -2.178 x 10-18 J ( );
 ERef = -2.178 x 10-18 J ( 𝟐 ) = 0, ( when n  ∞ ) 𝒏𝒇 𝒏𝒊𝟐
∞
 Ephoton = DE = hn = h (c / l );
 The radius of the first orbit r1 = 0.53 Å ( Bohr radius )
 The radius of the n-th orbit: rn = n2 r1 Examples (of emission) :
 The energy of the first level ( with n = 1, called Ground state):  n = 5 to n = 2; DE = 434 nm (blue)

E1 = -2.1278 x 10-18 J = -13.6 eV;  n = 4 to n = 2; DE = 486 nm (blue-green)

 The energy of the nth level (with n > 1, called Excited state ):  n = 3 to n = 2; DE = 657 nm (red)
𝑬𝟏
En =
𝒏𝟐
Prof. Xiao-Yuan Li, Dept. of Chemistry, HKUST
Section 2.1: The Bohr model of atomic structure: shell-like “orbits”

Bohr Model’s success :

 Correctly postulated that the energy of electron in atoms is quantized.
(i.e., electrons in atoms can only adopt certain fixed energies).
 Correctly fits the quantized energy levels of the hydrogen atom,
(i.e., nicely explained the experimentally observed H atomic spectra).

Bohr Model’s failures : Niels Bohr

(1885 –1962, Danish)
 It did not and cold not explain why the energy of electron is quantized! Nobel Prize in Phys 1922
 failed to explain the atomic spectra of multi-e atoms.
(It only works for H atom or atomic ions containing one electron! ). 2D-disk-like 3D-sphere-like
 It failed to account for the wave behavior of electron in atom.
(In other words, it still did not explain the particle-wave duality of electrons in atoms).
 It wrongly requires electron to move in circular orbits of fixed radii!
 It is actually inconsistent with the theory of electrodynamics at the time.
 The atoms would be 2D-“disk-like”, not 3D-“sphere-like”, and display anisotropic behaviors.
 It actually does not in any way tell how many electrons each orbit can accommodate and why!
Call for a better theory (or model) for a more accurate description of atomic structure !!
 quantum mechanical model (the modern view) of atomic structure. Prof. Xiao-Yuan Li, Dept. of Chemi
Section 2.2: Quantum mechanical model of atomic structure: atomic orbitals

In this section, we discuss and learn the 5th Model,

 The essence of quantum mechanical theory. (the modern view)

 Quantum mechanical (QM) model of atomic structure: Atomic Orbitals.

 Atomic orbitals: how are they obtained ?
 Atomic orbitals: how to understand them ?  Ignore all the Math!
 Focus on the Graphs!
 Atomic orbitals: how to represent them ?
 Atomic orbitals: how are they different from Bohr model’s circular orbits ?
 Limitation of QM model of atomic structure: certain precautions.

Kind Reminding Note:

The Schrodinger equation for hydrogen atom, its solving procedure, and the mathematical
forms of the solutions (i.e., math functions for atomic orbitals) are NOT required for this
course. They are mentioned in this section TO SERVE ONE PURPOSE only: to give you a
brief and simplified account on how the atomic orbitals (AOs) and their associated three
quantum numbers (QNs) and graphic representations are actually obtained or where they come
from. Of particular importance is to pay attention to the limitations of atomic orbital concept
in modern chemistry.

Prof. Xiao-Yuan Li, Dept. of Chemistry, HKUST

Section 2.2: Quantum mechanical model of atomic structure: atomic orbitals

Quantum mechanical model of atomic structure: some primary notes

 Our modern theoretical picture about atomic structure, or more specifically, about the
electron behavior in atoms, is from Quantum Mechanics (also known as quantum theory
or quantum physics ) which is a branch of physics dealing with physical phenomena at
microscopic scales (the length scales of atoms and molecules, as well as the electrons in
them).
 Quantum mechanical model of atomic structure provides a mathematical description of
electrons’ behavior in atoms, including both particle-wave duality and energy quantization.
In this description, an electron (a particle with rest mass) in atom behaves like a 3D-
standing wave oscillating around the atomic nucleus.
 In quantum mechanical model of atomic structure, the spatial motion of electrons is
governed by Schrodinger equation, and described by wave-functions which are also called
“atomic orbitals”. Atomic orbitals (i.e., wave-functions) are obtained as the solution to the
Schrodinger’s equation. Each atomic orbital has a characteristic energy associated with it.
The atomic orbitals can be used to find out or to calculate the probability of finding any
electron of an atom in any specific region around the atom's nucleus at a given energy.
 In another words, an atomic orbital from Quantum Mechanics depicts the electron’s
spatial occurrence probability around atomic nucleus at a given energy.

Prof. Xiao-Yuan Li, Dept. of Chemistry, HKUST

Section 2.2: Quantum mechanical model of atomic structure: atomic orbitals

Quantum mechanical model of atomic structure:

 Four fundamental aspects.
 Electrons, like all other particles with rest masses, display
wave behaviors; (l = h/p; n = E/h; de Broglie hypothesis, 1924)
 The motion of electron is described by wave-functions (called
atomic orbitals), and governed by the Schrodinger equation;
Each and every atomic orbital has a characteristic energy Louis de Broglie, Erwin Schrödinger
1892 –1987, French 1887–1961, Austrian
associated with it (called the energy of atomic orbital); Nobel Prize in Phys. 1929. Nobel Prize in Phys. 1933
(𝐇෡ Y(x,y,z) = E Y(x,y,z) ; Schrodinger equation, 1926 )

 The atomic orbital, when squared, describes the probability of

finding the electron at a spatial location; Therefore,
an atomic orbital is simply the probability amplitude
function. ( |Y(x,y,z)|2; Born’s rule, 1926 )
 There exists an intrinsic and fundamental limit to the precision
with which certain pairs of physical properties
Max Born Werner Heisenberg
of a particle, such as position x and momentum p, can 1882 –1970, German-British 1901-1976, German,
be known (or measured) simultaneously; Nobel Prize in Phys. 1954 Nobel Prize in Phys, 1932
𝒉
( Dx. Dp ≥ ; Heisenberg uncertainty principle, 1927 )
𝟒𝝅

Prof. Xiao-Yuan Li, Dept. of Chemistry, HKUST

 Section 2.2: Quantum mechanical model of atomic structure: atomic orbitals

z
Quantum mechanical model of atomic structure:
 How to obtain atomic orbitals? Solving the Schrodinger eqt. for H atom!
y
 Schrodinger equation:
(the equation of motion for electron in atom and molecule) x
෡ Y(r, q, f) = E Y(r, q, f)
𝐇
H atom in spherical
෡ is Hamiltonian (mathematical operator for energy):
𝐇 polar coordinates

ħ𝟐 𝒆𝟐 Notes :
෡ = KE + PE = [-
𝐇 𝛁2 ] + [- ]  KE =
𝒑𝟐
, ( p = mv )
𝟐μ 𝟒𝝅𝜺𝟎𝒓 𝟐𝒎
 de Broglie hypothesis
𝝏
𝝏𝟐 𝝏𝟐 𝝏𝟐  px = - i ħ
where 𝛁2 = + 𝟐+ 𝟐 = 𝝏𝒙
𝝏𝒙𝟐 𝝏𝒚 𝝏𝒛
𝟏 𝝏 2𝝏 𝝏 𝝏 𝟏 𝝏𝟐
= [sinq (r ) + 𝒔𝒊𝒏θ + ]
𝒓𝟐𝒔𝒊𝒏θ 𝝏𝒓 𝝏𝒓 𝝏θ 𝝏θ 𝒔𝒊𝒏θ 𝝏ϕ𝟐

Prof. Xiao-Yuan Li, Dept. of Chemistry, HKUST

 Section 2.2: Quantum mechanical model of atomic structure: atomic orbitals

Quantum mechanical model of atomic structure: Radial function

 How to obtain atomic orbitals ? Angular function
 Solutions to Schrodinger equation (atomic orbitals):
The Schrodinger equation is solved with two conditions : Colatitude function
(i) Separating the equation of 3-variables into three equations, one for each variable,
so that the final solutions have the form : Azimuthal function
Y(r, q, f) = R(r) Y(q, f) = R(r)P(q) F(f)
(ii) The solution of each one-variable equation requires the introduction of one boundary
condition (the constraint on wavefunctions), so that the final solutions have the form :
Y𝒏,𝒍,𝒎𝒍 (r,q,f) = 𝑹𝒏,𝒍 (r) 𝒀𝒍,𝒎𝒍 (q,f) = 𝑹𝒏,𝒍 (r) 𝑷𝒍,𝒎𝒍 (q) 𝑭𝒎𝒍 (f)
For radial function R(r), solutions exist if and only if an integer n = 1, 2, 3, … .
For colatitude function P(q ), solutions exist if and only if an integer l = 0, 1, 2, 3, … n-1 for each n.
z For azimuthal function F(f), solutions exist if and only if an integer ml = -l, -l+1, …l-1, l for each l.

Wavefunctions or
y Atomic orbitals
x
Prof. Xiao-Yuan Li, Dept. of Chemistry, HKUST
 Section 2.2: Quantum mechanical model of atomic structure: atomic orbitals
z
Let’s summarize and recall:
How are atomic orbitals obtained ? y
 Unlike the motion of the earth around the sun which is governed by the
equations of Newton’s laws, the motion of electron in atom is, by postulate,
x
governed by Schrodinger equation(S.E.), and the state of electron in atoms is
described by wavefunction,Y (x, y, z) which is obtained by solving the S.E.
𝐇෡ Y(x, y, z) = E Y(x, y, z) in Cartesian coordinates H atom in spherical
Or, ෡ Y(r, q, f) = E Y(r, q, f) in spherical polar coordinates
𝐇 polar coordinates

 The Schrodinger equation for H atom (1 electron only) can be solved and the explicit forms
of Y(x, y, z), the wavefunctions, be obtained only when certain boundary conditions are met
Y𝒏, 𝒍, 𝒎𝒍 (r,q,f) = 𝑹𝒏,𝒍 (r) 𝒀𝒍, 𝒎𝒍 (q,f) = 𝑹𝒏,𝒍 (r) 𝑷𝒍, 𝒎𝒍 (q) 𝑭𝒎𝒍 (f)
𝟏
𝐄𝐧 = - 𝑬𝟎 𝒘𝒉𝒆𝒓𝒆 𝑬𝟎 = 27.2 eV
𝟐𝒏𝟐
 “n” can adopt positive integers, n = 1, 2, 3, ……;
 for each and every “n”, l can take n different values, l = 0, 1, 2, 3, … n-1.
 for each and every “l”, ml can take (2l +1) different values, ml = -l, -l+1, …l-1, +l.
 Each and every wavefunction, Y𝒏, 𝒍, 𝒎𝒍 (r,q,f), is called an atomic orbital; And each and every
atomic orbital is associated with a unique set of integers (n, l, ml ), called quantum numbers.

Prof. Xiao-Yuan Li, Dept. of Chemistry, HKUST

Section 2.2: Quantum mechanical model of atomic structure: atomic orbitals

!! CAUTION !!
 Schrodinger equation in quantum theory is a postulate, not a law!
 Schrodinger equation that we have been referring to so far is for
H-atom (containing 1 electron ) only.
 The quantization of electron energy (and angular momentum) in H-
atom is the natural result of the solutions of Schrodinger equation.

 The interpretation of the physical meaning of atomic orbitals (wave-

functions) is from the Born’s rule, another hypothesis independent
of the Schrodinger equation and its solutions.

Prof. Xiao-Yuan Li, Dept. of Chemistry, HKUST

Section 2.2: Quantum mechanical model of atomic structure: atomic orbitals
z
Quantum mechanical model of atomic structure:
 How to obtain atomic orbitals ? y

 Examples of H-atom atomic orbitals (wavefunctions): x

Y𝒏, 𝒍, 𝒎𝒍 (r,q,f) = 𝑹𝒏,𝒍 (r) 𝑷𝒍, 𝒎𝒍 (q) 𝑭𝒎𝒍 (f) H atom in spherical
polar coordinates

Yn, l, ml n l ml Rn, l (r) Pl, ml (q) Fml (f)

𝟐 𝟏 𝟏
Y100 1 0 0 𝒆−𝒓/𝒂𝟎
∛𝒂𝟎 √𝟐 √𝟐𝝅
𝟏 𝒓 −𝒓/𝟐𝒂 𝟏 𝟏
Y200 2 0 0 [𝟐 −
𝒂𝟎
]𝒆 𝟎
√𝟐 √𝟐𝝅
𝟐√𝟐∛𝒂𝟎
𝟏 𝒓 −𝒓/𝟐𝒂 √𝟔 𝟏
Y210 2 1 0 𝒆 𝟎 cos q
𝟐
𝟐√𝟔∛𝒂𝟎 𝒂𝟎 √𝟐𝝅
𝟏 𝒓 −𝒓/𝟐𝒂 √𝟑 𝟏
Y211 2 1 1 𝒆 𝟎 sin q 𝒆±𝒊∅
𝟐√𝟔∛𝒂𝟎 𝒂𝟎 𝟐 √𝟐𝝅

Note: n = 1, 2, 3, … ; For each n, l = 0, 1, 2,… (n-1); For each l, ml = 0, ±1, ±2, …± l .

Prof. Xiao-Yuan Li, Dept. of Chemistry, HKUST
 Section 2.2: Quantum mechanical model of atomic structure: atomic orbitals
z
Quantum mechanical model of atomic structure:
 How to obtain atomic orbitals ? y
 Examples of H-atom atomic orbitals (wavefunctions): x
Y𝒏, 𝒍, 𝒎𝒍 (r,q,f) = 𝑹𝒏,𝒍 (r) 𝑷𝒍, 𝒎𝒍 (q) 𝑭𝒎𝒍 (f) H atom in spherical
polar coordinates

Yn, l, ml n l ml Rn, l (r) Pl, ml (q) Fml (f)

𝟐 𝒓 𝒓𝟐 −𝒓/𝟑𝒂 𝟏 𝟏
Y300 3 0 0 𝟐𝟕 − 𝟏𝟖 + 𝟐 𝟐 𝒆 𝟎
𝟖𝟏√𝟑∛𝒂𝟎 𝒂 𝟎 𝒂 𝟎 √𝟐 √𝟐𝝅
𝟒 𝒓 𝒓 −𝒓/𝟑𝒂 √𝟔 𝟏
Y310 3 1 0 𝟔− 𝒆 𝟎 cos q
𝒂𝟎 𝒂 𝟎 𝟐
𝟖𝟏√𝟔∛𝒂𝟎 √𝟐𝝅
𝟒 𝒓 𝒓 −𝒓/𝟑𝒂 √𝟑 𝟏 ±𝒊∅
Y311 3 1 1 𝟔− 𝒆 𝟎
𝟐
sin q 𝒆
𝟖𝟏√𝟔∛𝒂𝟎 𝒂𝟎 𝒂 𝟎 √𝟐𝝅

𝟒 𝒓𝟐 −𝒓/𝟑𝒂 √𝟏𝟎 𝟏
Y320 3 2 0 𝒆 𝟎 (3 cos2q – 1)
𝟖𝟏√𝟑𝟎∛𝒂𝟎 𝒂𝟎𝟐 𝟒 √𝟐𝝅
𝟒 𝒓𝟐 −𝒓/𝟑𝒂 √𝟏𝟓 𝟏 ±𝒊∅
Y321 3 2 1 𝟐
𝒆 𝟎
sin q cos q 𝒆
𝒂
𝟖𝟏√𝟑𝟎∛𝒂𝟎 𝟎 𝟐 √𝟐𝝅
𝟒 𝒓𝟐 −𝒓/𝟑𝒂 √𝟏𝟓 𝟏
Y32𝟐 3 2 2 𝟐
𝒆 𝟎
sin2 q 𝒆±𝒊𝟐∅
𝒂
𝟖𝟏√𝟑𝟎∛𝒂𝟎 𝟎 𝟒 √𝟐𝝅
Note: n = 1, 2, 3, … ; For each and every n, l = 0, 1, 2,… (n-1); For each and every l, ml = 0, ±1, ±2, …±l .
Prof. Xiao-Yuan Li, Dept. of Chemistry, HKUST
Section 2.2: Quantum mechanical model of atomic structure: atomic orbitals

Quantum mechanical model of atomic structure: |Y100(r,q,f)|2

(cross-section of a 3D plot)
 How to understand atomic orbitals ?
r
Example : “Y100” atomic orbital (wavefunction) occupied by the electron ⨁
𝟐 𝟏
in the ground state of H atom: Y100(r,q,f) = ( 𝒆−𝒓/𝒂𝟎 )( )
∛𝒂𝟎 𝟐√𝝅

 Electron probability density graph in 3D-space: | Yn,l,ml (r,q,f) |2 at every

R10(r)
point p(r, q, f), where Yn, l, ml (r,q,f) = Y1,0,0 (r,q,f) = R1,0(r)Y0,0(q,f) .
𝟐
 The radial probability amplitude graph: R10(r) = 𝒆−𝒓/𝒂𝟎 vs. r .
∛𝒂𝟎
⨁
 The radial probability (density) graph: |R10(r) |2 vs. r . r (Å)

 The radial probability distribution graph: 4pr2|R10(r) |2 vs. r .

|R10(r)|2
𝟏
 The angular function graph: Y00(q,f) = ( ) vs. (q, f) at a given r.
𝟐√𝝅

 The angular probability graph: Y002(q,f) vs. q, f , at a given r. ⨁

r (Å)
 rmax = a0 = 0.529 Å (Bohr radius!)

4pr2|R10(r)|2
rmax = 0.529 Å
 raverage > rmax
Y002(q,f) Y00(q,f)
Question: What is the conceptual difference between the Bohr radius ⨁
in Bohr model and in QM model? r (Å)
(2D vs. 3D, fixed r vs. variable r, position vs. probability..…) Prof. Xiao-Yuan Li, Dept. of Chemistry, HKUST
 Section 2.2: Quantum mechanical model of atomic structure: atomic orbitals

|Y100(r,q,f)|2 cross-section
⨁ r
To look at atomic orbital vs. ( r, q, f ) of a 3D plot

from both sides of nucleus

Example: “Y100” atomic orbital Y100(r,q,f)
vs. r
Y100(r,q,f) = R10(r) Y00(q,f) ⨁
𝟐 𝟏
= (∛𝒂 𝒆−𝒓/𝒂𝟎 )( 𝟐√𝝅 )
𝟎

Represented by |Y100(r,q,f)|2
the shape of Y00(q,f) at a given r : vs. r

The choice of (q, f ) is irrelevant for the 4pr2.|Y100(r,q,f)|2

vs. r
r-dependence of Yn00 !

⨁
Prof. Xiao-Yuan Li, Dept. of Chemistry, HKUST
Section 2.2: Quantum mechanical model of atomic structure: atomic orbitals

|Y210(r,q,f)|2
Quantum mechanical model of atomic structure: ( cross-section
 How to understand atomic orbitals ? of 3D plot ) ⨁ z r
Example : “Y210” atomic orbital (wavefunction) occupied by the electron
in the first excited state of H atom
𝟏 𝒓 −𝒓/𝟐𝒂 𝟏 𝟑
Y210(r,q,f) = ( 𝒆 𝟎 )( √ cosq )

R21(r)
𝟐√𝟔∛𝒂𝟎 𝒂𝟎 𝟐 𝝅

 Electron probability density graph in 3D-space: |Yn,l,ml (r,q,f)|2 at every

point p(r, q, f), where Yn,l,ml (r,q,f) = Y2,1,0 (r,q,f) = R21(r) Y10(q,f) .
𝟏 𝒓 −𝒓/𝟐𝒂 ⨁
 The radial probability amplitude graph ( R21(r) = 𝒆 𝟎 vs. r )
𝟐√𝟔∛𝒂𝟎 𝒂𝟎

|R21(r)|2
 The radial probability graph ( |R21(r) |2 vs. r ).
 The radial probability distribution graph ( 4pr2|R21(r) |2 vs. r ).
 The angular function graph ( Y10(q,f) vs. (q, f ) at a given r ).
⨁
 The angular probability graph ( Y10 2(q,f) vs. (q, f ) at a given r ). Y10(q,f)

4pr2|R21(r)|2
z

* Location(s) where Y =0 (therefore |Y|2 =0 ) is called the node. Y102(q,f)

⨁
Prof. Xiao-Yuan Li, Dept. of Chemistry, HKUST
Section 2.2: Quantum mechanical model of atomic structure: atomic orbitals

|Y210(r,q,f)|2 ⨁ +z cross-section
To look at atomic orbital vs. ( r, q, f ) of a 3D plot
from both sides of nucleus
Example: “Y210” atomic orbital
Y210(r,q,f) ⨁
+ Y has a
“sign” issue
Y210(r,q,f) = R21(r) Y10(q,f)
vs. r -
𝟏 𝒓 −𝒓/𝟐𝒂 𝟏 𝟑
=( 𝒆 𝟎 )( √ cosq )
𝟐√𝟔∛𝒂𝟎 𝒂𝟎 𝟐 𝝅

Y2 does not
Represented by |Y210(r,q,f)|2
have a
the shape of Y10(q,f) at a given r: vs. r “sign” issue

-z +z

4pr2|Y210(r,q,f)|2 “node” retains

Note: For the graphs on the right, q = 0 along +z in Y, Y2,
vs. r and 4pr2Y2
( or q = 180 along –z) is selected.
⨁

Prof. Xiao-Yuan Li, Dept. of Chemistry, HKUST

Section 2.2: Quantum mechanical model of atomic structure: atomic orbitals

Quantum mechanical model of atomic structure: |Y(r, q, f)|2

 How to represent atomic orbitals “graphically”?
 Atomic Orbital [ Y(r, q, f) ] is a wavefunction which is a probability
amplitude function, not a probability density (|Y(r, q, f)|2) function.
 Atomic Orbital has values ranging from r 0 to r  ∞, making it 𝒓
impossible to rigorously define the size of an atomic orbital. ‫| 𝟎׬‬Y(r, q, f)|2dt
= 0.9.
 Atomic Orbital however can be “represented” either as a probability
amplitude graph[ Y(r, q, f) , with sign or phase ] or as a probability
density distribution graph [ |Y(r, q, f)|2 , without sign or phase ].
 Atomic orbital is normally represented by a wavefunction graph
(probability amplitude graph) , that when square-integrated, enclosing
𝒓
90% of the total electron probability, ‫| 𝟎׬‬Y(r, q, f)|2dt = 0.9.
 Since the shape and orientation of an atomic orbital is determined by its
angular function Y(q,f) =P(q)F(f), the AOs are most often represented Y(q, f)
graphically by drawings of the angular function graph with signs indicated.
 Example: A hydrogen atom’s Y210 (or 2pz )atomic orbital is represented by
a dumbbell-shaped graph ( Y10(q,f) ) as indicated on the right.

Keep in Mind: Yn, l, ml(r,q,f) = Rn, l(r) Yl, ml(q,f)

Prof. Xiao-Yuan Li, Dept. of Chemistry, HKUST
Section 2.2: Quantum mechanical model of atomic structure: atomic orbitals

Let’s recall:
How to represent an atomic orbital ?
|Y210(r,q,f)|2
Atomic Orbital = Y𝒏, 𝒍, 𝒎𝒍 (r,q,f) = 𝑹𝒏, 𝒍 (r) 𝒀𝒍, 𝒎𝒍 (q, f) z
 Represented by an exact(math.) wave-function: R2,1(r) Y1,0(q,f)
y
𝟏 𝒓 −𝒓/𝟐𝒂 𝟏 𝟑
Example: Y210(r,q,f) = ( 𝟐√𝟔∛𝒂 𝒆 𝟎) ( √ cosq )
𝟎
𝒂𝟎 𝟐 𝝅

 Represented by a set of three quantum numbers: Section: 2.3

Example: Y210(r,q,f) = (n, l, ml) = ( 2, 1, 0 )

 Represented by a graph ( Y𝒏,𝒍,𝒎𝒍 (r,q,f) represented by the graph of Yl, ml(q,f) ): Section: 2.4

Example: Y210(r,q,f) represented by the graph of Y10(q,f)

These two representations of AOs will be used in this course !

Prof. Xiao-Yuan Li, Dept. of Chemistry, HKUST

 Section 2.2: Quantum mechanical model of atomic structure: atomic orbitals

Quantum mechanical model of atomic structure:

 What is the conceptual difference between the circular orbits in Bohr model
and the atomic orbitals in QM model of atomic structures ?

Bohr’s atom QM atom

1s orbital

+
-
2s orbital
+ +
n=1 +
n=2
n=3
n=4
-
2p orbital

electron in orbits with electron in atomic orbitals + -

fixed radii and fixed energies
around the nucleus
without fixed radii but with fixed energies
oscillating around the nucleus as a wave - +
(each “ orbit ” is a 2D-disk-like circle) (each orbital is a 3D-standing-wave) 3d orbital

Each “shell” (each “n”) Each “shell” (each “ n ”) *represented as 2D drum membrane
corresponds to one “orbit” contains to n2 “orbitals” vibration modes.
Prof. Xiao-Yuan Li, Dept. of Chemistry, HKUST
Section 2.2: Quantum mechanical model of atomic structure: atomic orbitals

Quantum mechanical model of atomic structure: how to think about atomic orbitals?
 Graphic representation ( Yl,ml for Yn,l,ml )

+/- + + -
- - +
1s orbital 2p orbital 3d orbital

 Static picture: “electron cloud” as electron probability density ( |Yn,l,ml|2 )

“thicker” vs. “thinner” region of cloud   larger vs. smaller probability density of electron occurrence.

 Dynamic picture: “oscillating standing wave” .

*represented as 2D drum membrane vibration modes.

Prof. Xiao-Yuan Li, Dept. of Chemistry, HKUST

Section 2.3: Atomic orbitals: quantum numbers
H atom
By far, we have learnt that
 The spatial motion of an electron around the nucleus in an atom is
q r e
described by wave-functions, Y(r, q, f), called atomic orbitals which ●
are obtained as the solutions of Schrodinger equation:
f
෡ Y(r, q, f) = E Y(r, q, f)
𝐇
 Each atomic orbital consists of 3 components, each of which is
3 spherical coordinates, r, q ,f,
associated with one spherical coordinate r, q, f, respectively:
are associated with 3 spatial
Y(r, q, f) = R(r)Y(q,f) = R(r) P(q) F(f) quantum numbers n, l, ml, of AOs

 Each spherical coordinate is associated with one integer called

quantum number, that dictates the constraint (quantization) of
electron’s motion along that coordinate.
Y𝒏,𝒍,𝒎𝒍 (r,q,f) = 𝑹𝒏,𝒍 (r) 𝑷𝒍,𝒎𝒍 (q) 𝑭𝒎𝒍 (f)
 Each atomic orbital, therefore the “spatial motion” of an electron
“in” that orbital, is completely specified once 3 quantum numbers,
n, l, ml , are specified.

In this section, we discuss three quantum numbers, Conversion between Cartesian

coordinates, x, y, z and the
n, l, ml , one-by-one, respectively. spherical coordinates, r, q ,f.

Prof. Xiao-Yuan Li, Dept. of Chemistry, HKUST

 Section 2.3: Atomic orbitals: quantum numbers

The Principle Quantum Number: n Yn, l, ml (r, q, f) = Rn, l(r) Pl, ml (q) Fml (f)
 n is introduced when solving Schrodinger equation to obtain R(r).
 n is associated with coordinate r, the distance between electron and
nucleus, therefore the size and energy of the orbital. It dictates the
restriction (and quantization) of electron’s motion along r coordinate.
+
 n can only take positive integer values, n = 1, 2, 3, ….∞.
 As n increases, the orbital becomes larger and more diffused, and
electron spends more time farther from the nucleus.

 As n increases, the orbital’s energy becomes higher (less negative),

and the electron is less tightly bound to the nucleus.
 The specific “shell” is associated with a given n value. Electrons in
different “shells” have different n values. The largest n value Dictates how atoms
corresponds to the outermost shell, and is called the “valence shell”.
bond with each other!!
The inner-shells are called “core shells”.
 In certain context, especially in the “modified” Bohr’s shell model
and in the periodic table, the following labels are sometimes used to
indicate the n value : n 1 2 3 4 5…

Symbol K L M N Xiao-Yuan Li,O…

Prof. Dept. of Chemistry, HKUST
 Section 2.3: Atomic orbitals: quantum numbers

The Angular Momentum Quantum Number: l Yn, l, ml (r, q, f) = Rn, l(r) Pl, ml (q) Fml (f)
(also called “orbital quantum number” in some textbooks )

 l is introduced when solving Schrodinger equation to obtain P(q).

 l is associated with coordinate q, the colatitude of the electron, and
e
therefore the “shape ” of the orbital. It dictates the restriction (and
quantization) of electron’s motion along q coordinate. +
 For each and every value of n, l can take integer values from 0 to n-1
(total n different values): l = 0, 1, 2, …. n-1.
 The value of l is associated with the magnitude of angular momentum
of electron’s spatial motion.
 Atomic orbitals with the same n but different l values have different shapes.
 Each l value is designated by a letter :

 Atomic orbitals having the same (n, l)

value are in the same “sub-shell”.

1 2 3 4
Section 2.3: Atomic orbitals: quantum numbers

The Magnetic Quantum Number: ml Yn, l, ml (r, q, f) = Rn, l(r) Pl, ml (q) Fml (f)
 ml is introduced when solving Schrodinger equation for F(f).
 For each and every value of l, ml can take integer values from
- l to +l ( total 2 l + 1 values): ml = -l, -l +1, …0,… l -1, l , e
or simply, ml = 0, 1, 2, ..  l.
+
 ml is associated with coordinate f, the azimuthal of the electron, and
therefore the orientation of the orbital. It dictates the restriction
(and quantization) of electron’s motion along f coordinate.
 ml is associated with the direction of the angular momentum. Its
value is associated with the magnitude of z-component of the
angular momentum.
 Atomic orbitals with the same n and l, but different ml values, have
the same energy, “same shape”* but different orientations.
 Atomic orbitals with same l but different ml are said in the
same sub-shell.

l=1 l=1 l=1

* : Please see text for a more detailed discussion on this point. ml = |±1| ml = |±1| ml = 0

Prof. Xiao-Yuan Li, Dept. of Chemistry, HKUST

 Section 2.3: Atomic orbitals: quantum numbers

Summary of the 3 quantum numbers that specify a given atomic orbital, therefore
the spatial motion of electron in that atomic orbital ( i.e., e’s orbital motion):
Quantum
number Symbol Quantized property Values Remark

Shell
Principle n Energy 1, 2, 3,……∞ ( energy and size of AOs )

Angular
Value of 0, 1, 2, 3…n-1 Subshell
l angular momentum (n values) ( shape of AOs )*
momentum
Orientation of 0, ±1, ±2,…±l Orientation of AOs *
Magnetic ml angular momentum (2l + 1 values) ( in a subshell )

Quantum Symbol Associated Associated Remark

number function in AO coordinate
Principle n Rn, l (r), radial r confinement and quantization
of e- along r

Angular l Pl, ml(q), colatitude q confinement and quantization

momentum of e- along q

Magnetic ml Fml(f), azimuthal f confinement and quantization

of e- along f
Prof. Xiao-Yuan Li, Dept. of Chemistry, HKUST
Section 2.3: Atomic orbitals: quantum numbers

Summary of the 3 quantum numbers specifying the orbital motions of electrons :

l = 0, 1, 2, 3…n-1 ml = 0, ±1, ±2, ± 3… ± l

“nl” (2l+ 1 )

1
4

16

The number of AOs at each Level ( or in each Shell ) = n2 !

Prof. Xiao-Yuan Li, Dept. of Chemistry, HKUST
 Section 2.3: Atomic orbitals: quantum numbers

Summary of the terminologies relevant to the 3 quantum numbers:

Quantum number Level, sublevel, and AOs Remark
( Shell, subshell, and AOs)
Principle ( n ) Atomic orbitals with the same n form a level (or a shell) has n2 atomic orbitals.
a Level (or a Shell)
Angular momentum ( l ) Atomic orbitals with the same n and l form a sublevel ( or a subshell) has (2l + 1)
a Sublevel ( or a Subshell) atomic orbitals.
Magnetic ( ml ) Orbitals with the same n, l, and ml refer to an atomic orbital is completely specified
the same orbital once the values of its n, l, ml are specified.

Quantum number Nodal surfaces on an AO Remark

( surfaces where Y = 0 ( i.e., |Y|2 = 0 )
Principle ( n ) An atomic orbital in level-n has total (n – 1) AOs in the same shell has the same
nodal surfaces. number of nodal surfaces
Angular momentum ( l ) An atomic orbital in sublevel l has l angular AOs in the same subshell has the
nodal surfaces. same number of angular modal
surfaces.
Magnetic ( ml ) An atomic orbital with specified n, l, ml, has a AOs in the same subshell also has
total (n – 1) nodal surfaces with (n – l – 1) radial the same number of radial nodal
nodal surfaces and l angular nodal surfaces. surfaces (n – l – 1).

Prof. Xiao-Yuan Li, Dept. of Chemistry, HKUST

 Let’s Recall: What We Have Learnt So far in This Section (Tue, 17-09-2019)

 What is an “atomic orbital” ?

Answer: a mathematical function! Y(x, y, z) or Y(r, q, f)

 How were “atomic orbitals” obtained?

Answer: as a set of solutions to Schrodinger equation! Y𝒏,𝒍,𝒎𝒍 (r,q,f) = 𝑹𝒏,𝒍 (r) 𝒀𝒍,𝒎𝒍 (q,f)

 What is the physical meaning of an “atomic orbital”?

Answer: by Born’s rule! |Y𝒏,𝒍,𝒎𝒍 (r,q,f)|2 = probability density of finding “e” at location (r,q,f).

 How to represent an “atomic orbital”?

Answer: by one of three alternative ways!
(i) by an Exact mathematical function! Y𝒏,𝒍,𝒎𝒍 (r,q,f) = 𝑹𝒏,𝒍(r) 𝒀𝒍,𝒎𝒍 (q,f)
(ii) or by a set of three integers ( n, l, ml ) !
(iii) or by a Graph of 𝒀𝒍,𝒎𝒍 (q,f)! + + + -
GOAL: - - +
1s 2py 3dxy
orbital orbital orbital

Prof. Xiao-Yuan Li, Dept. of Chemistry, HKUST

 Section 2.3: Atomic orbitals: quantum numbers

Designation (label) for atomic orbitals in a Subshell:

 Atomic orbitals in a subshell are specified by 2 quantum numbers: ( n, l )
(Keep in mind: there are (2 l + 1) different atomic orbitals in each subshell !)
n = 2, energy & size n = 3, energy & size
e.g.
nl 2p 3d
l = 1, shape l = 2, shape
 When we say “2p atomic orbitals”, we refer to atomic orbitals in 2p subshell.
( there are (2l + 1) = 2x1 +1 = 3 AOs in 2p subshell! ).
When we say “3d atomic orbitals”, we refer to atomic orbitals in 3d subshell.
( there are (2l + 1) = 2x2 +1 = 5 AOs in 3d subshell!).

 The designation of atomic orbital(s) in a subshell specifies the relative energy, size,
and especially the shape of AO! (but not the orientation of the AOs !)

Prof. Xiao-Yuan Li, Dept. of Chemistry, HKUST

 Section 2.3: Atomic orbitals: quantum numbers

Designation (label) for a specific atomic orbital:

 An atomic orbital is specified by 3 quantum numbers: ( n, l, ml )
n= 2 n= 3
e.g.
𝑛𝑙𝑚𝑙 2p-1 ml = -1 3d-1 ml = -1

l=1 l=2
 An atomic orbital is specified more commonly by 2 quantum numbers ( n, l )
and an orientation label “q” in Cartesian coordinate system(q is related to ml !):
n = 2, energy & size n= 3
e.g.
𝑛𝑙𝑞 2px orientation along
x axis, |ml| = 1.
3dxz orientation on
xy plane, |ml| = 1

l = 1, shape l=2
where “q” is in Cartesian coordinates, and is a linear term such as x, y or z for l =1, a quadratic term such
as z2, x2-y2, xy, xz, yz for l =2, and a cubic term such as xyz, or z3, etc. for l = 3.
Prof. Xiao-Yuan Li, Dept. of Chemistry, HKUST
 Section 2.3: Atomic orbitals: quantum numbers

Designation ( label ) for a specific atomic orbital:

 Relationship between two designations of atomic orbitals: nlml vs. nlq.

For s orbital ( l = 0 ): (n, l, ml) nlml nlq Example

( n, 0, 0 ) ns ns 1s

For p orbital ( l = 1 ): (n, l, ml) nlml nlq Example

( n, 1, 0 ) np0 npz 2pz 2p0,
(n, 1, ±1) np+1 , np-1 npx, npy 2px, 2py 2p1, 2p-1

For d orbital ( l = 2 ): (n, l, ml) nlml nlq Example

( n, 2, 0 ) nd0 ndz2 3dz2 3d0
(n, 2, ±1) nd+1, nd-1 ndxz, ndyz 3dxz, 3dyz 3d1,3d-1
(n, 2, ±2) nd+2, nd-2 ndxy, ndx2-y2 3dxy, 3dx2-y2 3d2, 3d-2

Note: There is NO one-to-one correlation between nlml and nlq atomic orbitals, except that for p orbitals,
|ml| =0 for pz, |ml| =1 for px and py; and for d orbitals, |ml| =0 for dz2, |ml|=1 for dxz and dyz, |ml|=2 for dxy
and dx2-y2 AOs. Prof. Xiao-Yuan Li, Dept. of Chemistry, HKUST
Section 2.3: Atomic orbitals: quantum numbers

!! CAUTION !!
 We have tried to explain WHERE each of the three quantum numbers n, l,
and ml comes from, WHAT values each of them are allowed to take, and
WHAT “physical picture” about an atomic orbital each of them corresponds
to. However we did NOT explain HOW these numbers are introduced and
WHY they can only take the specified values.

 To answer the questions of “HOW and WHY”, we have to do it mathematically

by solving the Schrodinger equation for H-atom explicitly and in a step-by-step
manner. That would need the knowledge of how to solve partial differential
equations under various boundary conditions, a math subject that will be learnt
in higher level math courses.

Prof. Xiao-Yuan Li, Dept. of Chemistry, HKUST

Section 2.4: Atomic orbitals: orbital shapes and relative energies

In this section, we discuss and learn the shapes (graphic

representations), relative energies, and degeneracy of atomic
orbitals in a shell ( n ) and a subshell ( l ):

 s orbitals ( l = 0 );
 p orbitals ( l = 1 );
 d orbitals ( l = 2 );
 f orbitals ( l = 3 ).

Prof. Xiao-Yuan Li, Dept. of Chemistry, HKUST

 Section 2.4: Atomic orbitals: orbital shapes and relative energies

“s” orbitals ( l = 0, the smallest being 1s )

 Spherical shape. Metal ball
for shot-put.
 The number of atomic orbitals (degeneracy) in s-subshell: (2l +1) = (2 x 0 + 1) = 1
 The number of nodal surfaces = n – 1.
(The total No. of nodes = n – 1 with the No. of “radial” nodes = n - l – 1, and No. of angular nodes = l )

1s |Ynlm|2 |Ynlm|2 Ynlm

1s
+
4pr2R2(r)

Radial probability 4pr2R2(r)

The electron probability The boundary surface The angular function
distribution representation representation representation
(no definite size) (0.9 the contour surface ) ( with phase indicated )

2s |Ynlm|2 Ynlm 2s
-+
⨁

|Ynlm|2 Ynlm
3s 3s
+
+ -

Prof. Xiao-Yuan Li, Dept. of Chemistry, HKUST

Section 2.4: Atomic orbitals: orbital shapes and relative energies

“p” orbitals ( l = 1, the smallest being 2p) :

 Dumbbell-shaped with two lobes.
 The number of atomic orbitals (degeneracy) in p-subshell : ( 2l + 1 ) = 3
dumbbells
 The number of nodal surfaces (nodes) in each orbital = n – 1.

2pz
+

Y(r)
⨁
z + - - +
+ -z
- +z
-
2pz Z(a0)
2px 2py

Radial probability 4p2R2(r)

1s
3pzy
3p

z 2p 2s
3d 3p 3s
3px 3py 3pz
The opposite signs are indicated by two colors! ⨁
np orbitals appear smaller than ns orbitals !

Prof. Xiao-Yuan Li, Dept. of Chemistry, HKUST

Section 2.4: Atomic orbitals: orbital shapes and relative energies

“d” orbitals ( l = 2, the smallest being 3d ) :

 For 3d AOs, two types of shapes: 4 with 4 lobes, and 1 with 2 lobes and a doughnut-shaped ring.
 The number of atomic orbitals (degeneracy) in d-subshell : (2l + 1 ) = 5
 The number of nodal surfaces (nodes) in each 3d orbital = n – 1 = 2
y y z

Radial probability 4pr2R2(r)

x x x

dxy dx2-y2 dz2

⨁

dxz dyz dxy dx2-y2 dz2

Prof. Xiao-Yuan Li, Dept. of Chemistry, HKUST

 Section 2.4: Atomic orbitals: orbital shapes and relative energies

“f” orbitals ( l = 3, the smallest being 4f ) :

 For 4f AOs, three types of shapes. 3 nodal
surfaces of
 The number of atomic orbitals (degeneracy) in f-subshell : (2l + 1 ) = 7 each f AOs
 The number of nodal surfaces (nodes) in each 4f orbital = n – 1 = 3. fz3
z

x y fxz2 fxyz
fy(y2-3x2) fyz2 fxz2
4f

Radial probability 4p2R2(r)

5d
6s
fz3
fx(x2-3y2) fxyz fz(x2-3y2)
⨁
Type-1: Type-2: Type-3:
6 lobes 8 lobes 2 lobes and two rings
 From your textbook Figure-2.18, an alternative but equivalent set;
 f-orbitals do not involve in chemical bonding because they are always “inner-shell” orbitals.
Prof. Xiao-Yuan Li, Dept. of Chemistry, HKUST
Section 2.4: Atomic orbitals: orbital shapes and relative energies

Atomic Orbital energy levels for H-atom (containing 1 electron only !) :

𝟏
 For H atom, the orbital energy depends ONLY on the principle quantum number, n. 𝐄𝐧 = - 𝑬𝟎
𝟐𝒏𝟐

 For each level of n (each shell), there are n2 atomic orbitals with the same energy. 𝑬𝟎 = 27.2 eV
( they are said to be degenerate; Or, for each shell, degeneracy = n2 )
Comparing with
 The lowest energy state = ground state( n= 1); The excited state (n > 1). Bohr model :
if energy n=3
matches DE12 n=2
n=1

No of AOs:
n2 = 32 = 9
energy
excited
No of AOs:
n2 = 22 = 4
state
……
No of AOs: n=3
n2 = 12 = 1 n=2
ground
n=1
state
n=3 if energy
n=2 matches DE13 excited
Comparing with n=1
state
Bohr model :

Prof. Xiao-Yuan Li, Dept. of Chemistry, HKUST

Section 2.5: Electron’s non-orbital motion: Spin and the Pauli Principle

Very much like the earth spins around its own axis when orbiting around the sun,
electrons also have spin motion in addition to their spatial orbital motion around the
nucleus.

The solar system: H atom: l s

e-
+

In this section, we discuss and learn

 The experimental evidences for the existence of electron spin;
 The establishment of the concept of electron spin;
 The spin quantum number ( S ) and the magnetic spin quantum number ( ms );
 The Pauli exclusion principle.

Prof. Xiao-Yuan Li, Dept. of Chemistry, HKUST

Section 2.5: Electron’s non-orbital motion: Spin and the Pauli Principle

 Experimental evidences for the existence of electron spin:

(1) The Stern–Gerlach experiment (1922):

Expected result:

Otto Stern
1888–1969, German,
Nobel Prize in Phys. 1943

Actual result:

Walter Gerlach
1889-1979, German This experiment suggests that the particles under this study possess an
intrinsic magnetic property that can take two and just two different states
(quantum behavior) under an external magnetic field. (Vaporized Ag atoms were
used in the first experiment by Stern and Gerlach ! ) Prof. Xiao-Yuan Li, Dept. of Chemistry, HKUST
Section 2.5: Electron’s non-orbital motion: Spin and the Pauli Principle

 Experimental evidences for the existence of electron spin:

(2) The fine structure in H emission spectrum(1887, Michelson & Morley):
Expected :

Observed :

This observation also suggests that electron in H atom possesses an intrinsic

quantum property that can adopt two and only two different states.

Prof. Xiao-Yuan Li, Dept. of Chemistry, HKUST

Section 2.5: Electron’s non-orbital motion: Spin and the Pauli Principle

 The establishment of the concept of electron spin :

Goudsmit and Uhlenbeck hypothesized in 1925 that the electron possesses an intrinsic angular
momentum - that is, spin, in addition to mass and charge. It is necessary to gave the quantized
spin angular momentum in order to account for the observed fine structure in H spectrum.

3s 3s

George Uhlenbeck
2p 2p Samuel Goudsmit
1900-1988, Dutch-American
1902-1978, Dutch-American
Wolf Prize in Phys. 1979
electron without spin electron with spin
( single line expected ) ( two lines observed)

Prof. Xiao-Yuan Li, Dept. of Chemistry, HKUST

Section 2.5: Electron’s non-orbital motion: Spin and the Pauli Principle

 The quantum numbers associated with electron spin :

 Spin angular momentum quantum number ( S ), and
 The magnetic spin quantum number (ms).
Experimental observations in the Stern-Gerlach experiment and the fine structure in hydrogen
emission spectrum suggest that an electron has an intrinsic magnetic angular momentum,
independent of its orbital angular momentum. These two experiments suggest there are two
and only two possible states for this property of electron, requiring an angular momentum
quantum number of 1/2.

Electron spin angular momentum quantum number ( S ): S = ½

( it defines the value or magnitude of spin angular momentum )

Magnetic spin quantum number ( ms ): ms = ± ½

( it defines the orientation of spin angular momentum )

In other words, an electron (or more accurately, its intrinsic magnetic

moment) can only take one of the two spin states, specified by
ms = +1/2 and ms = -1/2, respectively.

Why ½ ? : ½ is the smallest fraction number that, upon flip, results in

a change of the smallest integer of 1 ( ħ ), i.e., [(+1/2) - (-1/2) ] = 1.
Prof. Xiao-Yuan Li, Dept. of Chemistry, HKUST
Section 2.5: Electron’s non-orbital motion: Spin and the Pauli Principle

 The Pauli Exclusion Principle

Statement: No two identical fermions (particles with half-integer
spin, e.g., electron) may occupy the same quantum state
simultaneously.
Or, no two electrons in a single atom can have the same set of four
quantum numbers, n, l, ml , ms..
Wolfgang Pauli
Or, any one atomic orbital can only hold up to two electrons of 1900 –1958, Austrian
Nobel Prize in Phys. 1945
opposite spins.
Example :

( n, l, ml, ms ) = ( 1, 0, 0, +1/2 )
1s orbital 1s orbital 1s orbital
Forbidden X Forbidden X Allowed √ ( n, l, ml, ms ) = ( 1, 0, 0, -1/2 )

two electrons are at two electrons are at

SAME quantum state!! DIFFERENT quantum state!!
Prof. Xiao-Yuan Li, Dept. of Chemistry, HKUST
 Section 2.5: Electron’s non-orbital motion: Spin and the Pauli Principle

Let’s Summarize: FOUR quantum numbers are required to completely specify

the state of an electron in atom, including both its orbital motion and spin motion.
Quantum
number Symbol Quantized property Values Remark

Shell
Principle n Energy 1, 2, 3,…… ( energy of AOs )
Orbital
motion

Angular Value of (orbital) 0, 1, 2, 3…n-1 Subshell

momentum l angular momentum ( n values ) ( shape of AOs )

Orientation of (orbital) 0, ±1, ±2,…±l Orientation of AOs

Magnetic ml angular momentum ( 2l + 1 values ) in a subshell
motion

Orientation of 𝟏 𝟏
+𝟐, -𝟐 Orientation of
Spin

Magnetic spin ms spin angular momentum

electron spin in AO

Therefore, the state of an electron in atom is completely specified once the four quantum
numbers describing its spatial motion (n, l, ml) and spin motion (ms) are specified.

Prof. Xiao-Yuan Li, Dept. of Chemistry, HKUST

Section 2.5: Electron’s non-orbital motion: Spin and the Pauli Principle

Summary: How many electrons can each sub-shell (sub-level) accommodate ?

Angular Subshell Degeneracy Total No. of

momentum symbol ( No. of AOs ) electrons Remark
( subshell ) (Pauli principle) (shape)

l=0 s 1 1x2=2 spherical

l=1 p 3 3x2=6 dumbbell

l=2 d 5 5 x 2 = 10 2 types of shapes

l=3 f 7 7 x 2 = 14 3 types of shapes

l=4 g 9 9 x 2 = 18 …….

l=l … ( 2l + 1 ) (2l + 1)x 2 l types of shapes

( except l = 0, spheric )

Prof. Xiao-Yuan Li, Dept. of Chemistry, HKUST

Section 2.5: Electron’s non-orbital motion: Spin and the Pauli Principle

Summary: How many electrons can each shell ( level ) accommodate ?

Principle Angular Magnetic quantum Total No. of

quantum number momentum number electrons Remark
( Shell ) ( No. of subshells ) ( No. of AOs ) ( Pauli principle )
(l=0)
n=1 s 1 ( = 1 2) 2 K shell
( l = 0, 1 )
n=2 s, p 1 + 3 ( = 22 ) 8 L shell
( l = 0, 1, 2 )
n=3 s, p, d 1 + 3 + 5 ( = 32 ) 18 M shell
( l = 0, 1, 2, 3 )
n=4 s, p, d, f 1 + 3 +5 + 7 ( = 42 ) 32 N shell
( l = 0, 1, 2, 3, 4 )
n=5 s, p, d, f, g 1+3+5+7+9 ( = 52 ) 50 O shell

n=n ( l = 0, 1,3 … n-1) 1+3+…+ (2n-1) = n2 2n2 ……

Prof. Xiao-Yuan Li, Dept. of Chemistry, HKUST

Section 2.6: Multi-electron atoms

ALL the new concepts (such as “atomic orbitals”) from the quantum mechanical
model of atomic structure that we have discussed so far were generated from
the analysis of H atom, atom that contains one and only one electron.
In this section, we will discuss and learn that to what extent, these concepts
generated from the study of H atom can be extended to the description of
atoms containing multi-electrons.

Specifically, we will discuss

 From H-atom to multi-e atoms: Precaution when using Atomic Orbitals (again!)
 The main challenge in dealing with multi-electron atoms: e-e correlation problem.
 Penetration effect and shielding (screening) effect.
 The relative order of the atomic orbital energies in multi-electron atoms.

Prof. Xiao-Yuan Li, Dept. of Chemistry, HKUST

Section 2.6: Multi-electron atoms

PRECAUTION (AGAIN !)
when applying atomic orbitals concept to the multi-electron atoms
 Schrodinger equation has exact analytical solutions ONLY for H-atom or H-like atoms
such as He+ (i.e. atoms containing 1 electron only). Therefore, the concept of atomic
orbitals (and their graphs) is accurate for H or H-like atoms only.
 For atoms containing more than one electron (multi-electron atoms), Schrodinger
equation has no exact solutions (therefore, no exact atomic orbitals as we have for H-
atom). Many approximations, sometimes quite crude approximations, have to be invoked
in order to obtain even approximate solutions (Therefore, the concept of atomic orbitals
for multi-e atoms becomes an approximate one !) .
 Therefore, precaution must be taken when applying the concept of “atomic orbitals”,
which is established for H-atom, to multi-electron atoms (all atoms except H!), especially
heavy atoms, as well as to the description of bonding (interaction between atoms) in
molecules by AOs.
 In molecular quantum mechanics, H-like orbitals are often replaced by other similar but
simpler math functions such as Slater-type-orbital (STO) or Gaussian-type-orbital
(GTO) for the convenience of computation, implying a further approximations in
theoretical description of (heavier) atoms in molecules.

Prof. Xiao-Yuan Li, Dept. of Chemistry, HKUST

Section 2.6: Multi-electron atoms

 The main challenge in dealing with multi-electron atoms: e-e correlation problem.

X
Let’s consider the simplest multi-electron atom: 𝟒𝐇𝐞 with 2 electrons
𝟐
 Three components to the total energy in the Schrodinger equation for He:
 Kinetic energy of electrons ( x 2);
 Potential energy from the attraction between electrons and nucleus (x 2 );
electrons in well-
 Potential energy from the repulsion between electrons ( x 1); defined orbits
Since the electron pathways are unknown, the e-e repulsion in the third term can not be
defined, making it impossible to solve the Schrodinger equation exactly. This is the case
for ALL multi-electron atoms. This is called the e-e correlation problem.
 Experimental evidence for e-e correlation(repulsion) in He: One 1s electron as a
(2D) standing wave
 He  He+ + e-; Ionization Energy, I.E.1 = 2372 kJ
 He+  He2+ + e- ; Ionization Energy, I.E.2 = 5248 kJ e-
r1
If the two electrons were un-correlated, one would expect that the first I.E and the
second I.E. are equal. Since I.E.1 < I.E.2, it can be concluded that somehow the 2nd 2+ r12 ?
electron in the atom is making it easier for the removal of the 1st electron in the
atom. This can be viewed as the evidence that the 2nd electron “screening” the
r2 e-
nucleus from the 1st electron. As a result, the effective nuclear charge (the electron-electron
attraction) that the 1st electron experiences is reduced. correlation

Prof. Xiao-Yuan Li, Dept. of Chemistry, HKUST

Section 2.6: Multi-electron atoms

 Shielding (screening) effect is the effective decrease in attraction between the nucleus
and electrons (often in the outermost shell), caused by repulsion of other electrons in the
atom. Shielding effect is therefore a consequence of electron-electron correlation (repulsion).

Example : Consider potassium atom

𝟑𝟗
K (atomic number 19).
𝟏𝟗𝐊
The outermost electron is K19+
subject to the “shielding
effect” from the rest electrons.
!!Caution!!

 For different shells (different n), electrons in the inner shells have larger shielding (screening)
effect to those in the outer shells (the outer shell electrons experience stronger shielding effect);
 For same shell but different subshell (same n, different l), electrons in AOs with larger l are
shielded more than those in AOs with smaller l, determined mainly by AO’s radial distribution
and shape (the electrons with larger l number experience stronger shielding effect), namely,
 shielding effect to other electrons, n s > n p > n d > n f, or
 shielding effect experienced, n s < n p < n d < n f.

Caution: We are using the picture of Bohr model but the terms/language of QM model to
explain the effect in multi-electron atoms for which neither Bohr model nor QM model is exact !
 8+

Section 2.6: Multi-electron atoms

 Penetration effect describes how effectively and probably electrons can get close to the
nucleus of atom. An electron’s penetration ability is determined by the AO’s wavefunction
(more specifically, radial function R(r) ), not by electron-electron correlation.
 For same shell, electrons in AOs with smaller l have larger penetration effect than
those in AOs with larger l, dictated mainly by the AO’s radial distribution, i.e.,
 penetration effect of electrons: n s > n p > n d > n f .
 For different shells, electrons with the same ( n + l ), the smaller n have larger
penetration effect; i.e., (n-1)p > ns (e.g., 2p > 3s); (n-2)d > (n-1)p > ns (e.g., 3d > 4p > 5s )

penetration 2p : (n + l) = 2 + 1 = 3
2s > 2p 3s > 3p > 3d 3d : (n + l) = 3 + 2 = 5
2p 3s :
4p :
(n + l) = 3 + 0 = 3
(n + l) = 4 + 1 = 5
2p
2s
3s

⨁
⨁
⨁
Section 2.6: Multi-electron atoms

 Consequence of Penetration effect: AOs in the same shell have different

energies!  Those with larger penetration effect would have lower energy.

For AOs in the same shell (same n),

 The penetration effect : n s > n p > n d > n f
 The AOs’ energy : Ens < Enp < End < Enf

8+

Atomic orbital energy levels Atomic orbital energy levels

of H atom ( 1 e- ) of multi-e- atoms

Penetration effect and Shielding effect will be the key(qualitative) arguments in the
explanation of the periodic trends in the next two sections.

Prof. Xiao-Yuan Li, Dept. of Chemistry, HKUST

Section 2.6: Multi-electron atoms

Penetration effect and Shielding effect: Electrons that have greater penetration
effect can get closer to the nucleus and therefore can effectively shield the nucleus from the
electrons that farther away to the nucleus. Therefore, these two effects, albeit dictated by
different origins, are causally related to each other.
 Electrons having greater penetration subject less shielding effect by other electrons.
 Electrons have greater penetration can experience larger effective nuclear charge;
 Electrons have greater penetration have lower (more negative) energy.

 Higher energy
 Smaller effective nuclear charge
 Greater “shielding effect”
 Greater effective nuclear charge

1s
n=1
 Greater “penetration effect”

2s
n=2
 Lower energy

⨁ 2p

3s
⨁
n=3

3p

Caution: Because of the penetration effect, the average size (radius)

3d of an atomic orbital is not
⨁
necessarily correlated with its energy! For example: r3s > r3p, but E3s < E3p !
Prof. Xiao-Yuan Li, Dept. of Chemistry, HKUST
 Section 2.6: Multi-electron atoms
 Consequence of Shielding effect + Penetration effect: Effective nuclear charge(Zeff )
experienced by electrons in an atom
For an electron in an atom with atomic number Z (therefore Z protons),
 when r  ∞ , Zeff 1 , since all the other (Z − 1) electrons are, on the average, between it and the
nucleus. ( no penetration effect, complete shielding effect ).
 when r  0, Zeff ≈ Z, since all the other (Z - 1) electrons are not in between it and the nucleus.
( complete penetration effect, no shielding effect ).
 when r is in some intermediate values, 0 < r < ∞, Zeff is somewhere between 8+ 1 and Z: 1 ≤ Zeff ≤ Z.
Thus the actual Zeff experienced by an electron in an atom depends on two factors:
(i) the spatial distribution of the (all) electrons dictated by AOs ( penetration effect ) .
(ii) the electron-electron repulsions of (all electrons) ( shielding effect )
Zeff and Z for the outermost electrons of the elements
in the first three rows of the Periodic Table
D (Zeff – Z)= smallest
D (Zeff – Z)= 0

Prof. Xiao-Yuan Li, Dept. of Chemistry, HKUST

 Section 2.7: The periodic table of elements and the Aufbau principle

The main objective of this section is to establish a relationship between the

structure of the Periodic Table of Elements and the Electronic Structures of
elements from QM model. We will we discuss and learn

 The Mendeleev periodic table of the chemical elements: the organization and grouping of
elements according to atomic weight(and their chemical behaviors).
 The modern periodic table of the elements and the quantum mechanical model of atoms;
 Aufbau principle: the energy principle in building up the elements’ electronic configurations;
 Madelung rule and Hund’s rule: the sequence in filling up AOs with electrons;
 The structure of the periodic table in terms of the electronic configurations of elements;
 The terminologies associated with the periodic table;

 Key chemical information contained in the periodic table.

Prof. Xiao-Yuan Li, Dept. of Chemistry, HKUST

Section 2.7: The periodic table of elements and the Aufbau principle

The Mendeleev periodic table of the chemical elements:

 It is a table to organize and classify elements into “groups” (sometimes also
called “families”) and “periods”. The table was originally constructed to
represent the patterns observed in the chemical properties of the elements,
by Mendeleev (1869, according to the atomic weights) and Meyer (1864,
according to the valency), respectively.
 Mendeleev's periodic table enjoyed more success and recognition (and more
credit) because it was based on atomic weight, closer to the modern Dmitri Mendeleev
1834 –1907 , Russian
periodic table based on the atomic number, and also because it successfully
predicted the properties of some missing elements and therefore facilitated
their discovery, such as Gallium (Ga) and Germanium (Ge).
 The quantum mechanical model(the 5th model) of atomic structure provides
a nice explanation for the success of the Mendeleev periodic table, and a
more rigorous foundation for the construction of the “modern periodic
table of elements” on the basis of the atomic number (not on atomic weight!).
Since for an element, the “Atomic Number” = “No. of Electrons”, the Julius von Meyer
structure of the Periodic Table will be correlated with the structures of 1830–1895, German
electron configurations of atoms.

Prof. Xiao-Yuan Li, Dept. of Chemistry, HKUST

Section 2.7: The periodic table of elements and the Aufbau principle

A Modern Period Table of The Elements Magic

Attention: Atomic number is the key ! Numbers:
Magic numbers: 2, 8, 8, 18, 18, 32...14, why ?
2

18

18

32

…
why ?

14

14
Prof. Xiao-Yuan Li, Dept. of Chemistry, HKUST
 Section 2.7: The periodic table of elements and the Aufbau principle

 The modern periodic table of the elements and the quantum mechanical
model of atomic structure:
In the modern periodic table of the elements, the elements are sequenced in
accordance with the increase of their atomic number, therefore, the increase of
the number of protons in atomic nuclei (or the number of electrons in atoms).
The electronic configuration of the elements (i.e., the arrangement of electrons in
elements) are determined by filling electrons in the hydrogen-like atomic orbitals
from the quantum mechanical model of atomic structure.
Aufbau(build-up) principle: The hypothetical process of “building-up” elements by
adding protons one by one to the nucleus while adding electrons one by one to the
hydrogen-like atomic orbitals. Electrons fill up the orbitals at the lower energy before those
with higher energies. (Implicit assumption: all elements have the same type of orbitals as
those obtained for hydrogen atom ! )
Two rules are followed in constructing the electronic configuration of elements by
following Aufbau principle:
 Madelung rule (for AOs with different energies) and Hund’s rule (for AOs with the same energy).

Prof. Xiao-Yuan Li, Dept. of Chemistry, HKUST

 Section 2.7: The periodic table of elements and the Aufbau principle

Madelung rule (1936): The sequence of adding electrons to hydrogen-like

atomic orbitals of multi-e atoms to obtain their electronic configurations, after
taking into consideration of the penetration and shielding effects:

(i) Orbitals with a lower ( n + l ) value are filled before those with higher ( n + l ) values;
Example: 4s AOs are filled before 3d AOs because ( n + l ) = 4 for 4s but 5 for 3d.
(ii) For orbitals with the same ( n + l ) values, those with lower n are filled first. Erwin Madelung
1881-1972, German
Example: 3d and 4p AOs both have ( n + l ) = 5, 3d are filled before 4p.

n = 7 7s 7p n = 7 7s 7p  7s 5f 6d 7p 32
6d  6s 4f 5d 6p 32
n = 6 6s 6p 6d n = 6 6s 6p
5p 5d 5f n = 5 5s 5p 5d 5f  5s 4d 5p 18
n = 5 5s
4p 4d 4f  4s 3d 4p 18
n = 4 4s 4p 4d 4f l=4 n = 4 4s l=4
 3s 3p 8
n = 3 3s 3p 3d

X
n = 3 3s 3p 3d l=3 l=3
 2s 2p

√
n=2 2s 2p 8
n=2 2s 2p l=2 l=2
 1s 2
n = 1 1s1s l=1 n = 1 1s1s l=1
Period No. of Elements
l=0 l=0 (n) in each period

Orbital energy levels of H atom (1e-) Orbital energy levels of multi-e atoms
(without penetration and shielding effects) (with penetration and shielding effects)
118 Total!

Prof. Xiao-Yuan Li, Dept. of Chemistry, HKUST

 Section 2.7: The periodic table of elements and the Aufbau principle

Atomic Orbital Energy Levels of Multi-e Atoms under Madelung Rule:

(with penetration effect and shielding effect!) 118 Total!
7p
6d 5f 7s 5f 6d 7p 32
7s
n=7 6p
5d 6s 4f 5d 6p 32
4f
6s
n=6
Energy of AOs

5p
4d 5s 4d 5p 18
5s
n=5 4p
3d
4s 3d 4p 18
4s
n=4 3p
3s 3p 8
3s
n=3
2p
2s 2s 2p 8
n=2
1s
n=1 1s 2
l=0 l=1 l=2 l=3 Period Elements
Subshell (Angular Momentum Quantum Number) (n) /period
Exceptions to Madelung rule: Madelung rule applies only to neutral atoms at their ground state. There
are quite a few exceptions, notably for elements preferring either a full or a half-full d subshells, e.g., Cu
(4s1d10 instead of the predicted 4s23d9) and Cr (4s1d5, instead of the predicted 4s23d4 ). Prof. Xiao-Yuan Li, Dept. of Chemistry
Section 2.7: The periodic table of elements and the Aufbau principle

Hund’s rule (1927): The electronic configuration with the lowest energy for
an atom is the one having the maximum number of parallel unpaired electrons
allowed by the Pauli exclusion principle in a particular set of degenerate
orbitals. (More rigorous statement: For a given electron configuration, the
term with maximum multiplicity has the lowest energy. The multiplicity is
equal to (2S +1), where S is the total spin angular momentum for all electrons.
The term with lowest energy is also the term with maximum S). Friedrich Hund
1896–1997, German
Example: Write down the electronic configuration and orbital diagram for nitrogen atom N.
(i) The atomic number of N is 7, therefore 7 electrons.
(ii) The electronic configuration of N is therefore, N: 1s22s22p3.
(iii) The orbital diagram for nitrogen according to Hund’s rule : Wrong!
Violate the Hund’s rule!

X
n = 7 7s 7p
n = 6 6s 6p 6d 1s 2s 2p
n = 5 5s 5p 5d 5f
n = 4 4s 4p 4d 4f l=4
n = 3 3s 3p 3d l=3
n=2 2s
n = 1 1s1s
2p
l=1
l=2
Correct!
Obey the Hund’s rule!
√
l=0

Prof. Xiao-Yuan Li, Dept. of Chemistry, HKUST

Section 2.7: The periodic table of elements and the Aufbau principle

Example : Construct the ground state electronic configuration of oxygen (O) and
show its orbital diagram.
Answer: (i) Oxygen atom has an atomic number of 8, and therefore 8 electrons.
(ii) The electronic configuration according to the Madelung rule is O: 1s22s22p4
(iii) According to the Hund’s rule, the orbital diagram is given by

n = 7 7s 7p 1s 2s 2p
√
n = 6 6s 6p 6d
n = 5 5s 5p 5d 5f
n = 4 4s 4p 4d 4f l=4 1s 2s 2p
n = 3 3s 3p 3d l=3
n=2 2s 2p l=2
n = 1 1s1s
l=0
l=1
X

Prof. Xiao-Yuan Li, Dept. of Chemistry, HKUST

Section 2.7: The periodic table of elements and the Aufbau principle

Example 2: Construct the ground state electronic configuration of sodium(Na) atom

Answer: (i) Sodium atom has an atomic number of 11,

n = 7 7s 7p
therefore 11 electrons.
n = 6 6s 6p 6d
(ii) The electronic configuration according to 5p 5d 5f
n = 5 5s
the Madelung rule is Na: 1s22s22p63s1 4p 4d 4f
n = 4 4s l=4
Since Neon atom has an electron configuration n = 3 3s 3p 3d l=3
of Ne: 1s22s22p6, we therefore can write the n = 2 2s 2p l=2
electron configuration of Na in an abbreviated n = 1 1s1s l=1
form as Na: [Ne]3s1
l=0
The electron configuration in the inner levels
(inner shells) are represented by the symbol of
the preceding inert element: e.g. Li : [He]2s1;
Ca: [Ar]4s2; etc.

Prof. Xiao-Yuan Li, Dept. of Chemistry, HKUST

Section 2.7: The periodic table of elements and the Aufbau principle

A Modern Period Table of The Elements Magic

Numbers:
 The sequence of elements according to the atomic number !
 Divided into “blocks” according to valence subshells.
 s block 2
 p block
 d block 8
 f block
8

18

18

32

32
why ?
14

14
Prof. Xiao-Yuan Li, Dept. of Chemistry, HKUST
 Section 2.7: The periodic table of elements and the Aufbau principle
The “block” structure of the periodic table from the electronic configurations of elements.
Shell l=0 l=1 Magic Electron
( n ): No.: Configuration:

n=1 2 1s1 ~ 1s2

n =2 8 2s1 ~ 2s22p6
l=2
n=3 8 3s1 ~ 3s23p6
n=4 18 4s1 ~ 4s23d104p6
n=5 18 5s1 ~ 5s24d105p6

n=6 32 6s1 ~ 6s24f145d106p6

n=7 32 …

l=3
La 14 4f1 ~ 4f14

Ac 14 5f1 ~ 5f14

Please recall the Aufbau principle and Madelung rule !

Prof. Xiao-Yuan Li, Dept. of Chemistry, HKUST
 p block elements:
Section 2.7: The periodic
s block elements:
table of elements and the Aufbau principle
 Non-metals
 Alkali metals
 Alkaline metals  Noble gases
 Halogens
The periodic table and the electronic configurations of elements:
 Chalcogens
1 2 3 4 5 6 d 7block 10
 Semi-metals
8 elements:
9 11 12 13 14 15 16 17 18
P 1 1s1 1s2
E H (1)  Transition
Check the configurations metals
by Madelung rule; He
R 2 2s1 2s2 (2)  Noble metals
Circle the exceptions, and discuss why; 2p1 2p2 2p3 2p4 2p5 2p6
Li Be B C N O F Ne
I
O 3 3s1 3s2 3p1 3p2 3p3 3p4 3p5 3p6
Na Mg Al Si P S Cl Ar
D
4s1 4s2 3d1 3d2 3d3 4s13d5 3d5 3d6 3d7 3d8 4s13d10 3d10 4p1 4p2 4p3 4p4 4p5 4p6
4 K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr
#
5s1 5s2 4d1 4d2 4d4 5s14d5 4d5 4d7 4d8 4d10 5s14d10 4d10 5p1 5p2 5p3 5p4 5p5 5p6
(n) 5
Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe

6s1 6s2 5d1 5d2 5d3 6s25d4 5d5 5d6 5d7 5d9 6s15d10 5d10 6p1 6p2 6p3 6p4 6p5 6p6
6 Cs Ba *La Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn

7s1 7s2 6d1 6d2 6d3 7s26d4 6d5 6d6 6d7 6d8 7s16d10 6d10 7p1 7p2 7p3 7p4 7p5 7p6
7 Fr Ra +Ac Rf Db Sg Bh Hs Mt Ds Rg Uub Uut Uuq f block elements:
Uup Uuh Uus Uuo

8s1 8s2  Rare earth metals

8 Uue Ubn  Nuclear metals
*5d1 5d14f1 4f3 4f4 4f5 4f6 4f7 5d14f7 4f9 4f10 4f11 4f12 4f13 4f14 4f145d1
La Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu

6d1 6d2 6d15f2 5f3 5f4 5f6 5f7 6d15f7 5f9 5f10 5f11 5f12 5f13 5f14 5f147p1
+Ac Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr

Prof. Xiao-Yuan Li, Dept. of Chemistry, HKUST

 Section 2.7: The periodic table of elements and the Aufbau principle
Terminologies from the periodic table and their relevance to the atomic electronic configurations :
Terminologies relevant to Relevance to the electronic configuration Remark
the Periodic Table of the elements
a Period (a row) Elements with the same n (the principle quantum number) Same shell

a Group (a column/family) Elements with the same l ( No. of valence electrons) Same subshell

Valence shell the outermost shell ( with the largest n) for chemical bonding

Core shell the inner shells ( n < nvalence ) K, L, M, N, O…. labels.

Main group elements Elements with nsa npb electrons in valence shell Representative elements

Transition metal elements Elements with (n-1)dm (m=1 to 9) electrons in (n-1) shell. Tends to form Mn+

Lanthanides series Elements with electrons in 4f subshell Rare earth (+ Sc and Y)

Actinide series Elements with electrons in 5f subshell Nuclear (radioactive)

Alkali metals Elements with ns1 in valence shell Tends to form M+1

Alkaline metals Elements with ns2 in valence shell Tends to form M+2

Noble(inert) gases Elements with full ns2np6 valencce shell. Inert elements

Halogens Elements with ns2np5 in valence shell Tends to form X-1

Chalcogens Elements with ns2np4 in valence shell Tends to form X-2

Prof. Xiao-Yuan Li, Dept. of Chemistry, HKUST

Section 2.7: The periodic table of elements and the Aufbau principle

113 114 115 116 117 118

Ds Rg Cn Nh Fl Mc Lv Ts Og

From now on, given a periodic table, you are expected to think about it and use it in
two alternatively ways:
(i) Traditional way: names, symbols, atomic numbers, atomic masses…….
(ii) Electronic configurations of valence shell: number and type of valence electrons
Section 2.7: The periodic table of elements and the Aufbau principle

Key information contained in the periodic table :

 Quantum mechanical model of atomic structure provided the basis for the
understanding of the structure and organization of the periodic table.
 Elements in the same period (the same row) have the same number of electron
shells (the same principle quantum number, n) but the different number of
electrons in the valence shell and the different electronic configurations of the
valence shell.
 Elements in the same group (the same column or the same family) have different
number of electron shells (the different principle quantum number, n) but the
same number of electrons in the valence shell and the same electronic
configuration of the valence shell.
 The periodic table is divided into s-block (l = 0), p-block (l =1) , d-block (l = 2),
and f-block (l =3), with each block characterized by the electronic configurations
in its valence subshells.
 From the location of an element in the periodic table (the period + the group), its
ground state electronic configuration can be written out by following the
Madelung rule (albeit with some exceptions ) and Hund’s rule.

Prof. Xiao-Yuan Li, Dept. of Chemistry, HKUST

Section 2.8: Periodic trends in atomic properties

In this section, we discuss and learn the trends in several important atomic
properties with reference to the periodic table, including

The observed atomic properties :

 Ionization energy ( I or IE ): Atom’s ability to withhold its own valence electron(s)
 Electron affinity ( EA ): Atom’s ability to grab external electron(s)
 Atomic size (radius)* ( ratom ): Atom’s ability to resist deformation and to spatially
accommodate neighboring atoms.

The non-observed(derived) atomic properties :

 Effective nuclear charge ( Zeff ) and shielding effect ( Sh = Z - Zeff )
 Metal character and nonmetal character
 Electronegativity (c ) (will be discussed in chapter 3!)

Prof. Xiao-Yuan Li, Dept. of Chemistry, HKUST

Section 2.8: Periodic trends in atomic properties

 Trend in Ionization Energy ( I or IE ):

Definition: Ionization energy of an atom (or ion) is the energy required to
remove an electron from a gaseous atom or ion in its ground state.
X(g) → X+(g) + e–
The first ionization energy (I1 or IE1) of an atom is an indication for how strong its nucleus
attract its valence electron( electron in the outmost shell ).
For example: For Mg atom ( [Ne]3s2 ), its ionization energies were measured as
Mg → Mg+ + e– I1 = 735 kJ/mol ( the 1st IE )
Mg+ → Mg2+ + e– I2 = 1445 kJ/mol ( the 2nd IE )
Mg2+ → Mg3+ + e– I3 = 7730 kJ/mol ( the 3rd IE )

Discussion : Note that Mg atom has two valence electrons ( 3s2 ).

The first two ionization energies (I1 and I2) are the removal of the valence
electrons (electrons in the outermost shell). The third ionization (I3) is the
removal of a core electron. The observation that I3 is much larger than I1
and I2 suggests that (i) the core electrons are bound much more tightly than
the valence electrons, and (ii) atom in a fully-filled shell (called the closed
shell) electron configuration is in a very stable condition.
“Closed shell” = Shell that is fully occupied by electrons. Prof. Xiao-Yuan Li, Dept. of Chemistry, HKUST
Section 2.8: Periodic trends in atomic properties
 Trend in the First Ionization Energies (IE1) for the representative
elements: s-block and p-block 1s2

2s22p6
2s2 2s22p1 2s22p3 2s22p4

 Filled subshells (ns2 and np6) are very stable with high IE1;
 Half-filled subshell ( np3 ) is more stable relative to the nearby non-half-filled configurations.
Prof. Xiao-Yuan Li, Dept. of Chemistry, HKUST
Section 2.8: Periodic trends in atomic properties
 Trend in the First Ionization Energies (IE1): 1s2

np6

np3

ns2
(n-1) d10

f14

Prof. Xiao-Yuan Li, Dept. of Chemistry, HKUST

Section 2.8: Periodic trends in atomic properties
 Trend in the First Ionization Energy (IE1): an overall picture

I
At

Prof. Xiao-Yuan Li, Dept. of Chemistry, HKUST

Section 2.8: Periodic trends in atomic properties

 Trend in the First Ionization Energy (IE1): A Summary

 In the same period from left to right, IE1 generally increases, with the smallest values
found for alkali metal and largest found for the inert gases, suggesting that elements
with a closed shell (the fully filled shell) is the most stable electronic configuration.

 In the same period from left to right, IE1 generally shows larger values for elements with
fully filled subshells, s2, p6, d10 and f14 relative to other nearby elements with similar
electronic configurations, suggesting that elements with a full subshell tend to show
higher stability.

 In the same period from left to right, IE1 generally shows larger values for the half-filled
subshells such as p3 and d5, comparing with the nearby elements with non-half-filled
subshells, suggesting that elements with such half-filled subshells tend to show higher
stability than nearby elements.

 In the same group from top to bottom, IE1 generally decreases, suggesting that for
elements with more shells (larger n), valence electrons are less strongly bounded to the
elements, and therefore easier to be removed (i.e., more unstable).

Prof. Xiao-Yuan Li, Dept. of Chemistry, HKUST

Section 2.8: Periodic trends in atomic properties

 Trend in Electron Affinity (EA):

Definition: Electron affinity is the energy change (normally “released”) associated
with the addition of an electron to a gaseous atom
X(g) + e– → X-(g)
Electron affinity of an atom is an indication for its ability to attract extra
(external) electron to its valence shell.

Examples: Cl (g) + e- → Cl-(g), EA = -348.7 kJ mol-1

Br (g) + e- → Br-(g), EA = -324.5 kJ mol-1
Na (g) + e- → Na-(g), EA = -53 kJ mol-1
K (g) + e- → K-(g), EA = -48 kJ mol-1
Caution: The negative values mean that the process releases energy and as a result,
the anions formed are stable with respect to the neutral atoms. A positive
EA value would mean that the element can not form stable X ion.
The halogens have much larger (more negative) EA than alkali metals,
indicating that the halogens have much bigger tendency to form stable anions
than the alkali metals do.

Prof. Xiao-Yuan Li, Dept. of Chemistry, HKUST

 Section 2.8: Periodic trends in atomic properties

 Trend in Electron Affinity (EA):

( - [Link]-1)
Cl
F Br
I
At

Au
Pt

Ag
Cu

 In the same period, the halogen element (ns2np5) has the highest EAs, suggesting
their highest tendency in acquiring extra electron to form anions.
 In the same period, the coinage metal (Cu, Ag, Au) [ (n-1)d10ns1] has the highest
EA among all the metals. Prof. Xiao-Yuan Li, Dept. of Chemistry, HKUST
Section 2.8: Periodic trends in atomic properties

 Trend in Electron Affinity (EA): s2p5

Low EA Elements:
 Fully-filled shell(closed shell)
Increase  Fully-filled subshell

s1d10  Half-filled subshell

s2p3
s1 s2d10 High EA Elements:
s2 s2d5 s2p6
 s2p5 (non-metals)
Increase

 s1d10 (transition metals)

 s1 (alkaline metals)
Attention to Exceptions :
 Small atoms in 2nd period
versus atoms of the same
group in other periods,
e.g., F vs. Cl, Br, I, At.
 Interpretation:
The role of e~e repulsion

Prof. Xiao-Yuan Li, Dept. of Chemistry, HKUST

Section 2.8: Periodic trends in atomic properties

 Trend in the Electron Affinity (EA): A Summary

 In the same period from left to right, EA generally increases; In the same group
from top to bottom, EA generally decreases.
 Elements with the closed shell ( fully filled shell) configurations have positive or
very small EA, suggesting that elements with a full shell tend to show very high
stability and have no tendency or very small tendency to acquire extra electron
to their valence shell.
 Elements with the half-filled subshells such as p3 or d5, have smaller EAs than
their nearby elements, suggesting that such elements tend to show higher
stability than their nearby elements.
 EAs are generally much larger for non-metals than for metals, with halogens
having the highest EAs in each period, and the coinage metals having the
highest EAs among metals.
 Pay attention to the exceptions of the elements in the second period where e~e
repulsion appears to have more pronounced effect.

Prof. Xiao-Yuan Li, Dept. of Chemistry, HKUST

 Section 2.8: Periodic trends in atomic properties

 Trend in Atomic Size ( atomic radius ):

Just as the boundary of the outermost atomic orbital(s) can not be defined
exactly, the size of atoms (and atomic ions) can not be defined exactly
as well.

non-M There are commonly four types of atomic radius used in chemistry :
Covalent radius (rcov): half the inter-nuclear distance in a molecule
with two identical (or similar) atoms bonded to each other.
M
Metallic radius (rmet): half the distance between the nuclei of two
adjacent atoms in a metallic element.
Noble
van der Waals radius (rvdW): half the inter-nuclear distance
between two non-bonded atoms in a solid.
ions
Ionic radius (rion): the ion’s share of the distance between cation
and anion in an ionic solid.
The atomic radii and ionic radii can be obtained by quantum mechanical
calculation as well. While the absolute values thus obtained may not be
accurate, their relative sizes do consistent with the experimental
estimated patterns and trends. M+ -- X-

Prof. Xiao-Yuan Li, Dept. of Chemistry, HKUST

 Section 2.8: Periodic trends in atomic properties

 Trend in Atomic Size ( covalent radius ) for the representative elements:

 Trend in the same period (from left to right):
( in unit of pm ) decrease. ( same “n”, different “ l “ )
n=1
 Trend in the same group (from top to bottom):
increase. ( different “n”, same “ l “ )
n=2
Three factors dictating atomic size :
 The number of the shells ( = the principle quantum
n=3 number, n). The more the shells, the larger the atoms
(from top to bottom in a group).
 The effective nuclear charge Zeff (  the atomic
n=4 number Z ). The higher the effective nuclear charge,
the smaller the atoms (from left to right in a period).

n=5  Shielding effect ( the number of shell). The larger

the shielding effect, the smaller the effective nuclear
charge. It therefore has a negative effect (partial
cancellation effect) to the factor Zeff. .
( From left to right in a period, shielding effect
n=6
decreases. From top to bottom in a group, shielding
effect increases. )
 Exception:
s-block p-block Ne is larger than F and O (e~e repulsion dominates)!
Section 2.8: Periodic trends in atomic properties
 Trend in Atomic Size ( the calculated atomic radii):

( Unit: pm )

 Generally speaking, the atomic sizes of metals are larger than that of the nonmetals, with the sizes of
semi-metals in between.
 The size variation of the transition metals are much smaller than that of the main group elements.

Prof. Xiao-Yuan Li, Dept. of Chemistry, HKUST

Section 2.8: Periodic trends in atomic properties
 Trend in Atomic Size (the covalent radii) :
 In each period, alkali metals
have the largest, noble gases
the smallest atomic radii.
 The more the shells, the larger
the elements.
 Above trends are exactly
opposite (anti-correlated ) to
that of IE1.

Trend in EI1

Prof. Xiao-Yuan Li, Dept. of Chemistry, HKUST

Section 2.8: Periodic trends in atomic properties

 Trend in the Atomic size: A Summary

 In the same period from left to right, the atomic size generally decreases, suggesting that
when the shell number remains the same, the effective attraction between the nucleus and
the outermost electrons increases with the increase of the atomic number. In each period,
the largest element is alkali metal and the smallest is noble gas.
 In the same group from top to bottom, the atomic size generally increases, suggesting that
when the shell number increases, the effective attraction between the nucleus and the
outermost electrons decreases.
 Generally speaking, the metals are much larger than nonmetals. The main group elements
show much larger size variation than transition metal elements.
 The trend of atomic size is opposite to that observed for the IE1 of the elements, suggesting
that the larger the atomic size, the smaller is the IE1, and easier it is to remove electron
from the atom.

Prof. Xiao-Yuan Li, Dept. of Chemistry, HKUST

Section 2.8: Periodic trends in atomic properties

Let’s Summarize: the Implicit Messages

 Put together, from the three measured atomic properties, we can obtain
the following physical insight about the atomic behaviors:
ATOMIC PROPERTY MEANING

First Ionization Energy (IE1) Atom’s ability to withhold its own outmost electron(s)

Electron Affinity (EA) Atom’s ability to grab external electron(s)

Atomic Radius (r) Atom’s ability to resist deformation and to spatially

accommodate neighboring atoms

 Implications:
 Atoms with larger IE1, larger EA, and smaller r  Stronger ability to compete for
electrons when forming chemical bond(s) by interacting with other atoms.
 Atoms with smaller IE1, smaller EA, and larger r  Weaker ability to compete for
electrons when forming chemical bond(s) by interacting with other atoms.

Prof. Xiao-Yuan Li, Dept. of Chemistry, HKUST

 Section 2.8: Periodic trends in atomic properties

 Trend in Effective Nuclear Charge ( Zeff ):

Definition: the average net positive charge experienced by an electron in a multi-electron
atom, taking into consideration of the “shielding effect ” by the electrons in the inner shells.
The term "effective" is used because the shielding effect ( Sh ) of the electrons in the inner
shells prevents the electrons in the outer shells from experiencing the full nuclear charge ( Z );
Sh.= Z - Zeff .

Factors affecting Effective Nuclear Charge ( Zeff ) :

(i) its atomic number (Z);
(ii) Sh is determined by the number of electrons in the shells and subshell “inner” to the
electron for which Zeff is to be estimated.
Caution:
 Zeff is not a measurable property of atom. Therefore, there is no unique way of defining its
scale and values.
 Zeff can be anti-correlated to (show opposite trend to) the strength of shielding effect.
 In the context of this course, and as a crude approximation, the Zeff experienced by an
electron in an atom can be estimated to be Zeff = Z - n(inner) where n(inner) is the total number
of electrons in the shells inner to the electron to be estimated.

Prof. Xiao-Yuan Li, Dept. of Chemistry, HKUST

 Section 2.8: Periodic trends in atomic properties

 Trend in Effective Nuclear Charge ( Zeff ):

 Zeff and Z for the outermost electrons of the elements of

the first three rows of the Periodic Table
 Zeff (valence) ≈ Z - n(inner)
D (Z – Zeff )= smallest
D ( Z – Zeff )= 0

Prof. Xiao-Yuan Li, Dept. of Chemistry, HKUST

Section 2.8: Periodic trends in atomic properties

Trends in metals character and nonmetal character (qualitative descriptor) :

 Metals are electropositive elements that have a tendency to lose or give away
their valence electrons and to form positively charged ions (called cations).
Na  Na+ + e-
Mg  Mg2+ + 2e-
 Non-metals are electronegative elements that have a tendency to gain extra
electrons and to form negatively charged ions (called anions) or share electrons
with other atoms.
Cl + e-  Cl-
O + 2 e-  O2-
 Metalloids are elements with properties that are intermediate between or a
mixture of those of metals and nonmetals, and which is considered to be difficult
to classify unambiguously as either a metal or a nonmetal. e.g., Si and Ge

Prof. Xiao-Yuan Li, Dept. of Chemistry, HKUST

Section 2.8: Periodic trends in atomic properties

Trends in metals character and nonmetal character :

 No. Elements: 118

 No. Metals: 91
 No. Nonmetals: 19
 No. Metalloids: 8

Prof. Xiao-Yuan Li, Dept. of Chemistry, HKUST

Section 2.8: Periodic trends in atomic properties

Trends of atomic properties : A summary

Ionization energy

Electron affinity
Atomic radius

Ionization energy
Electron affinity
Atomic radius

 Pay special attentions to the exceptions in each trend;

 Most of the exceptions can be accounted for by electronic configurations of the elements involved;
 Stability order: full shell > full sub-shell > half-subshell > non-of-above.
Section 2.8: Periodic trends in atomic properties

Trends of atomic properties: a summary

In this section, we have discussed the periodic trends of three observed
properties of elements ( IE, EA, ratom ) and two derived properties of elements
(Zeff, M/non-M characters ) with reference to the periodic table.

The key factor which affect the periodic trends can be considered as the
effective nuclear charge ( Zeff ), which is, in turn, determined by

 The “formal” nuclear charge ( Z, i.e., the atomic number ),

 The number of shells ( n, which is also  the atomic radius ),
 The subshells or the radial/angular distribution of AO (the penetration effect),
 The electron-electron repulsion or correlation(the shielding effect).

Prof. Xiao-Yuan Li, Dept. of Chemistry, HKUST

Section 2.8: Periodic trends in atomic properties

Key Information from the Periodic Table

 It is the number and type of valence electrons that primarily determine
an atom’s chemistry.
 Elements in the same group ( the same column) have the same number
and type of valence electrons, and the same ground state electronic
configuration, and therefore are expected to display similar chemical
behaviors.
 Elements in the same block (e.g., s-block ) are expected to be chemically
more similar to each other than with the elements in other blocks.

Prof. Xiao-Yuan Li, Dept. of Chemistry, HKUST

Section 2.9: The properties of selected groups: alkali metals and halogens

Prof. Xiao-Yuan Li, Dept. of Chemistry, HKUST

Section 2.10: Key concepts checklist

Key concepts checklist :

 Bohr model of atomic structure: shell-like “orbits” and energy quantization

 Quantum mechanical model of atomic structure: atomic orbitals

 Atomic orbitals: quantum numbers

 Atomic orbitals: shapes and energies

 Electron’s non-orbital motion: spin and the Pauli principle

 Multi-electron atoms: Main challenges and assumptions

 The periodic table: structure, electronic configurations, terminologies (for the first 4 periods of 36 elements)

 Period trends in atomic properties: IE, EA, ratom; Zeff, metallic/nonmetallic character.

 The properties of two representative groups: alkalis (metals) and halogens (nonmetals)

Prof. Xiao-Yuan Li, Dept. of Chemistry, HKUST

Chem 1020: General Chemistry IB

END

Prof. Xiao-Yuan Li, Dept. of Chemistry, HKUST

Section 2.10: The properties of selected groups: alkali metals

Prof. Xiao-Yuan Li, Dept. of Chemistry, HKUST

 Section 2.10: The properties of selected groups: alkali metals

Due to their ns1 valence shell configuration, they have a strong tendency to lose their
single valence electron to form a stable close shell cation (M+). As a result,
 They are the most chemically reactive of the metals with the reactivity increasing from top
to bottom.
 They have the lowest first ionization energy, lowest electron affinity, largest atomic radii and
lowest electronegativity of any period.
 They are powerful reducing agents (with strong tendency to donate or give away electrons).
 They often display +1 oxidation state in the compounds, producing the MX monohalides
and the M2O oxides.

* Electro- **EA
negativity: ( kJmol-1)

0.98 -59.6
0.93 -52.9
0.82 -48.4
0.82 -46.9
0.79 -45.5

* Comparing with the reference value of H = 2.2, and that of Cl = 3.0

** Comparing with that of Cl = -349 [Link]-1
Prof. Xiao-Yuan Li, Dept. of Chemistry, HKUST
Section 2.10: The properties of selected groups: alkali metals

 Some common applications of alkali metals

Lithium batteries
(such as LiCoO2):

Table salt
(NaCl)

Baking soda Soda ash Caustic soda

(NaHCO3) (Na2CO3) (NaOH)

Fertilizer and Cesium formate

gunpowder (Cs+HCO2-)
(KNO3)

Prof. Xiao-Yuan Li, Dept. of Chemistry, HKUST

Section 2.10: The properties of selected groups: halogens

Prof. Xiao-Yuan Li, Dept. of Chemistry, HKUST

 Section 2.10: The properties of selected groups: halogens

Due to their ns2np5 valence shell configuration, they have a strong tendency to acquire
an extra electron to form a stable close shell anion (X-). As a result,
 They are chemically very reactive nonmetals;
 They are of highest electron affinity and electronegativity of any period;
 They are very strong oxidizing agents (i.e., with strong tendency to obtain an extra electron);
 They often display -1 oxidation state in ionic compounds (such as NaCl), and producing
monoacids HX.

Element electron Element Density M.P. B.P. IE1 * EA Covalent Ionic **Electro
config. state (g. cm-3) (C) (C) ([Link]-1) ([Link]-1) radius (pm) radius (pm) negativity
F 2s22p5 F2 (g), Pale 1.50 -220 -188 1681 -328 71 133 4.0
(Fluorine) yellow-green

Cl 3s23p5 Cl2 (g) 2.03 -101 -34 1251 -349 99 181 3.0
(Chlorine) pale green

Br 4s24p5 Br2 (l ) 3.12 -7 59 1140 -325 114 196 2.8

(Bromine) red

I 5s25p5 I2 (s), 4.93 114 184 1008 -295 133 220 2.5
(Iodine) purple

* Comparing with that of Na = -52.9 [Link]-1

** Comparing with the reference value of H = 2.2, and that of Na = 0.93. F has the highest electronegativity of all elements.
Prof. Xiao-Yuan Li, Dept. of Chemistry, HKUST
Section 2.10: The properties of selected groups: halogens

 Some common applications of halogens :

In toothpaste
( NaF )

Table salt Iodized table salt

(NaCl) ( NaCl / KI)

Photographic film Tincture of iodine

(AgBr) (I3-)

Prof. Xiao-Yuan Li, Dept. of Chemistry, HKUST