Contents

1 Atomic Structures 2
1.1 Atom . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
1.1.1 The concept of atom . . . . . . . . . . . . . . . . . . . . . . . . . 2
1.1.2 The structure of the atom . . . . . . . . . . . . . . . . . . . . . . . 2
1.1.3 Atomic Number, Mass Number, and Isotopes . . . . . . . . . . . . 3
1.1.4 Periodic Table . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
1.2 Electron Configuration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
1.2.1 Atomic spectrum of hydrogen . . . . . . . . . . . . . . . . . . . . . 5
1.2.2 Quantum mechanics . . . . . . . . . . . . . . . . . . . . . . . . . . 6
1.2.3 Atomic Orbitals . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
1.2.3.1 solution of Schrodinger equation for hydrogenic atoms . . 8
1.2.3.2 Shells, subshells, and orbitals . . . . . . . . . . . . . . . . 8
1.2.3.3 The radial variation of atomic orbitals . . . . . . . . . . . 9
1.2.3.4 The angular variation of atomic orbitals . . . . . . . . . . 10
1.2.3.5 The other quantum numbers Electron spin . . . . . . . 12
1.2.4 The Build-up Principle . . . . . . . . . . . . . . . . . . . . . . . . 12
1.2.4.1 Penetration and shielding . . . . . . . . . . . . . . . . . . 12
1.2.4.2 Build-up Principle . . . . . . . . . . . . . . . . . . . . . . 14
1.3 Atomic parameters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
1.3.1 Atomic and ionic radii . . . . . . . . . . . . . . . . . . . . . . . . . 16
1.3.2 Ionization Energy . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
1.3.3 Electron Affinity . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
1.3.4 Electronegativity . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
1.3.5 Polarizability . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
1.4 Homework questions I (from Atkins book): . . . . . . . . . . . . . . . . . 22

1
Chapter 1

Atomic Structures

1.1 Atom
1.1.1 The concept of atom
In the 5th century B.C., Greek philosopher Democritus: all matter consists of very
small, indivisible particles atomos.
In 1808, John Dalton atomic theory (marked the beginning of the modern era of
chemistry)

Elements are composed of extremely small particles called atoms.

All atoms of a given element are identical, having the same size, mass, and
chemical properties. The atoms of one element are different from the atoms of
all other elements.
Compounds are composed of atoms of more than one element. In any com-
pound, the ratio of the numbers of atoms of any two of the elements present
is either an integer or a simple fraction.
A chemical reaction involves only the separation, combination, or rearrange-
ment of atoms. It does not result in their creation or destruction.

An atom is the basic unit of an element that can retain the chemical properties and
involve in chemical reaction.

1.1.2 The structure of the atom

The electron: discovered by J. J. Thomson using cathode ray tubes in 1897. Elec-
trons are negatively charge particles, and e/m ratio is -1.76 108 C/g.

Protons and nucleus discovered by Rutherford in 1910

2
CHAPTER 1. ATOMIC STRUCTURES 3

Neutrons: James Chadwick 1932.

Rutherfords atomic model

The main subatomic particles:

Charge
Particle Mass (g) Coulomb Charge Unit
Electron 9.10939 1028 -1.6022 1019 -1
Proton 1.6726210 24 +1.6022 +1
1019
24
Neutron 1.67249310 0 0

1.1.3 Atomic Number, Mass Number, and Isotopes

The identification of an element is determined by the number of protons in the
atom.
Atomic number (Z) = number of protons in nucleus.
Mass number (A) = number of protons + number of neutrons=atomic number (Z)
+ number of neutrons.
The same element has the same atomic number (i.e. number of protons), but can
have different numbers of neutrons (isotope).
For example:11 H, 21 H (D), 31 H (T), 235 238
92 U, 92 U

1.1.4 Periodic Table

More than half of the elements known today were discovered between 1800 and 1900.
With many elements discovered, scientist started to recognize the periodic regularities in
physical and chemical properties. (see figure below) The observation of periodicity among
elements led to the development of a periodic table, a table in which the elements are
grouped and arranged according to their chemical and physical properties.
CHAPTER 1. ATOMIC STRUCTURES 4

Classification of elements

Metallic elements: lustrous, malleable, ductile, and electrically conducting

Nonmetals: gases, liquids, or solids that do not conduct electricity.
Metalloids: silicon

First periodic table, Dmitri Mendeleev, 1869. Arranged the known elements in
order of increasing atomic weight (molar mass) The arrangement led to group the
elements with similar chemical properties into a group. For example, C, Si, Ge, and
Sn.
At the same time, Lothar Meyer in Germany arranged the elements according to
their physical properties. (see above figure)

Using Periodic table to predict or rationalize trends in the physical and chemical
properties. For example, R2 C=CR2 suggests the R2 Si=SiR2 , and was isolated in
1981.
Modern periodic table: arranged according to the atomic number (Z); periods,
groups; main-group (representative) elements (s- and p-blocks), transition metal
elements (d-block), Lanthanides (f-block, lighter), and actinides (f-block, heavier)
CHAPTER 1. ATOMIC STRUCTURES 5

1.2 Electron Configuration

According to Rutherfords experiment, the center of the atom is composed of nucleus
(protons + neutrons). The volume of the nucleus is very tiny, and the rest of the atom
is pretty much empty space. The electrons are wondering around the empty space in an
atom. When chemical reaction occurs, different atoms interact with each other, and we
can image the interactions start with the electrons of different atoms. It is important
to know how the electrons move in an atom, or how do we describe the electrons in the
atom. Modern quantum mechanics provide a way to answer the question. We will start
with hydrogen spectrum.

1.2.1 Atomic spectrum of hydrogen

Hydrogenic atoms: hydrogen-like atoms (or ions) that have only one electron, so free of
the complicating effects of e-e repulsion.
CHAPTER 1. ATOMIC STRUCTURES 6

In the emission spectrum of hydrogen gas, the emission is found to consist of a series
of discrete lines in the UV, visible, and IR regions.
1
Johann Rydberg equation: = R( n12 1
n22
), where R is the Rydberg constant
1
7 1
(=1.09710 m )
Lyman series: n1 =1; Balmer series: n1 =2; Paschen series: (n1 =3); Brackett series:
n1 =4.
Bohrs atomic model

Key assumption: electrons can only have specific (quantized) energy values at
discrete radius (called orbits). En = R( n12 )
Light is emitted as e moves from one energy level to a lower energy level
Bohrs atomic model explains the hydrogen atomic spectrum well, but failed
to explain the spectra of elements with more than one electrons.

1.2.2 Quantum mechanics

Bohrs atomic model of electrons with discrete orbits surrounding the nucleus could not
explain the atomic spectrum of many elements, and eventually replaced by the quantum
mechanics developed by Erwin Schrodinger and Werner Heisenberg in 1926. Here are
several concepts related to quantum mechanics.
The quantum of energy: Energy is discrete, and quantum is the smallest quantity
of energy. E = hv = hc/ (Plancks constant =6.63 1034 Js)

The dual nature of the electron: (De Broglie, 1926) Electron has both wave and
h
particle properties. = mu . The diffraction pattern of the electrons (Thomson and
Davisson) is explained by the possibility of finding an electrons with certain energy,
i.e. the wave of electron is a possibility wave associated with energy.
Example 1: An electron has a mass of 9.11 1031 kg and a charge of 1.602 1019
C. Calculate the de Broglie wavelength of an electron that has been accelerated by
a potential of 50 V.
CHAPTER 1. ATOMIC STRUCTURES 7

In the quantum world, it is not possible to know simultaneously both the momen-
tum p (mv) and the position of a particle with certainty (Heisenberg uncertainty
principle). In other words, classic mechanics can not be used to describe the world
of an atom. According to Heisenberg uncertainty principle, the electrons does not
h
orbit the nucleus in well-defined path. xp 4

Schrodinger equation.

wavefunction, , is a mathematical function of the position coordinates, and

is
h used to describe the ibehavior of an electron in an atom.
2
2 2 2
8h2 m 2 + V (x, y, z) (x, y, z) = E(x, y, z), i.e., x2 + y 2 + y 2 +
8 2 m
h2 (E V (x, y, z)) = 0
In the Schrodinger equation, the physically acceptable solutions exist only for
certain value of E, i.e., quantization of energy.
Probability density 2 : proportional to the probability of finding an electron
at a given location. i.e., the2 d =2 dxdydz is proportional to the probability
of finding the electron in that volume d .

Wavefunction has regions of positive and negative amplitude, or sign. The inte-
ractions between wavefunctions can be constructive interference or destructive
interference.

CHAPTER 1. ATOMIC STRUCTURES 8

1.2.3 Atomic Orbitals

The wavefunction of an electron in Schrodinger equation is called atomic orbital. In
chemistry, we use the visual representation of the wavefunction (i.e. atomic orbital).
Here, we discuss briefly the mathematics forms of the wavefunction.

1.2.3.1 solution of Schrodinger equation for hydrogenic atoms

Since the potential in hydrogenic atom is spherically symmetric ( Z/r), the solution is
expressed in terms of the spherical polar coordinates, as shown below.

In these coordinates, the orbitals (wavefunctions) all have the form
nlml = Rnl (r)Ylml (, )
The allowed energies are given by
2
m e e4
En = hcRZ
n2 , with n = 1, 2, 3, ..., and R = 8h3 c20
The wavefunction solution indicates that the atomic orbitals of hydrogenic atoms is
uniquely labeled by a set of three integers n, l, ml , which are called quantum numbers.
n : principle quantum number, specifies the energy of the orbital

hcR=13.6 eV, and the the zero of energy corresponds to the electron and
nucleus have no interaction with each other.

l: angular momentum quantum number, indicates the angular shape of orbitals

ml , magnetic quantum number, indicates the orientation of the orbital.
Electron spin, s.

1.2.3.2 Shells, subshells, and orbitals

In a hydrogenic atom, the set of orbitals with the same n have the same energy, and
are said to be in the same shell. The principle quantum number defines a series
of shells of the atom.

The orbitals belonging to each shell are classified into subshells according to the
quantum number l.

The quantum number l can have the values l=0, 1, ..., n-1 for a given value of
n.
For example, for n=1, only one subshell with l=0 (s); for n=2, two subshells
with l=0 (s), 1(p).
Value of l 0 1 2 3 4 ...

Orbital s p d f g ...
CHAPTER 1. ATOMIC STRUCTURES 9

Individual orbitals: a subshell with quantum number l consists of 2l+1 individual

orbitals. These orbitals are distinguished by the third quantum number ml , where
ml change from l to l.
Example: Identifying orbitals from quantum numbers: Which set of orbitals is
defined by n=4 and l=1? How many orbitals are there in this set?

1.2.3.3 The radial variation of atomic orbitals

In the spherical polar coordinates, the orbitals have the following form for hydrogenic
atom,
nlml = Rnl (r)Ylml (, )
The solution indicates that the wavefunction can be written as the product of a
function R(r) of the radius and a function Y (, ) of the angular coordinates.
The radial wavefunction R(r) expresses the variation of the orbital with distance
from the nucleus. The location where R(r) passes through zero are called radial
nodes.
The angular wavefunction expresses the orbitals angular shape. The planes on
which the angular wavefunction passes through zero are called nodal planes or
angular nodes.
Table: Hydrogen orbitals

The radial wavefunctions

All orbitals decay exponentially at sufficiently great distance from the nucleus.
An orbital has n l 1 radial nodes, i.e. the radial wavefunction crosses
zeron l 1 times.
CHAPTER 1. ATOMIC STRUCTURES 10

All orbitals except s orbitals are zero at the nucleus, as a consequence of the
absence of orbital angular momentum.

The radial distribution function: gives the probability that an electron will be found
at a given distance from the nucleus, regardless of the direction.

As we discussed earlier, 2 gives the probability density of electrons, and the

total probability of finding the electrons in space is the integral of 2 d =2 dddr
.
The total probability of finding the electron in a spherical shell of
radius r and
thickness dr is the integral of 2 d over all angles of and , i.e. 2 dddr =



r 2
r
R (r)Y 2 (, ) = P (r)dr.



P (r) = R2 (r) Y 2 (, ) is called the radial distribution function, which
gives the probability that an electron will be found at r from the nucleus,
regardless of the direction.
In general, P (r) = r2 R2 (r).A radial distribution function for an orbital in a
shell of principle quantum number n has n l peaks, and the outermost peak
being the highest.
In hydrogenic atoms, for 1s orbital, the distance at which the electron is most
likely to be found is rmax = aZ0 , where a0 is Bohr radius, a0 = 0 ~2 me e2 =52.9
pm. (Figure1.13)
Example 1.3. Figure 1.14 shows the radial distribution function for 2s and 2p
hydrogenic orbitals. Which orbital gives the electron a great probability of
close approach to the nucleus?

1.2.3.4 The angular variation of atomic orbitals

The orbital is normally represented by the boundary surface, which defines the
region of space within which there is a high (typically 75%) probability of finding
the electron.
s-orbital (Figure 1.15): spherical, no nodal plane.

p-orbital (Figure 1.16): 1 nodal plane, px , py , pz . positive (+) and negative (-).
d-orbital (Figure 1.17) and f-orbital (Figure 1.18).
In general, an orbital with the quantum number l has l nodal plane.
CHAPTER 1. ATOMIC STRUCTURES 11