ATOMIC STRUCTURE

CHEM 121 Lecture 1

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STRUCTURE OF THE ATOM

There are two regions

The nucleus
• With protons and neutrons
– Positive charge
– Almost all the mass

Electron cloud
– Most of the volume of an atom
– The region where the electron can be found
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SUBATOMIC PARTICLES

Name Symbol Charge Relative Mass Actual Mass, g

electron e- -1 1/1837 9.11 x 10-28
proton p+ +1 1 1.67 x 10-24
nuetron no 0 1 1.67 x 10-24

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THE PERIODIC TABLE

Mendeleev and Meyer :

organized elements in order of their atomic weights

identified groups of similar properties

able to predict properties of still unknown elements

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THE MODERN PERIODIC TABLE

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 The Circular
Periodic
Table of the
Elements

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Dalton’s Atomic Theory

Matter consists of small particles called atoms

All elements are made up of atoms

Atoms are indivisible and indistructable

Atoms of a given element are identical in mass and in all other

properties

A compound is formed when the atoms of two or mole elements

combine.

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Dalton’s Atomic Theory

Matter consists of small particles called atoms

All elements are made up of atoms
Atoms are the smallest unit of matter that retains thephysical and
chemical properties of the element, however they are divisible by
non-chemical means.

2. All atoms of a single element contain the identical number of

protons and electrons, however their masses may vary with number
of neutrons.

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DISCOVERY OF SUBATOMIC PARTICLES

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 Millikan Oil-
Drop
Experiment

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Rutherford’s Thin
gold foil
experiment

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 In 1913, Mosley suggested the idea of the neutron but its was in
1932 that James Chadwick bombarded the element Be with alpha
particles, an experiment that help him detect the suggested neutron.

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DSCOVERY OF SUBATOMIC PARTICLES

Each element emits light of specific energies when excited by an electrical

discharge

Balmer: Energies of the visible light emitted by H atom are given by the
equation:

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BOHR’s MODEL OF THE ATOM

Electrons are moving in circular orbits around the positively charged nucleus
without loss or gain of energy.

Electrons may absorb (or emit) light of a specific energy and be excited (or fall
back) to orbits of higher (or lower) energy.

Accurately predicts energy levels of H and Hydrogen like ions but failed with 2
or more electrons

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Some Quantum Mechanics
Louis de Broglie(1924): Electromagnetic radiation could be considered
to consist of particles called photons yet at the same time exhibit wave-
like properties, such as interference and diffraction, then the same
might be true of electrons.

This dual nature is called wave–particle duality .

A consequence of duality is that it is impossible to know the linear

momentum (the product of mass and velocity) and the location of an
electron (or any other particle) simultaneously. This restriction is the
content of Heisenberg’s uncertainty principle , that the product of the
uncertainty in momentum and the uncertainty in position cannot be less
than a quantity of the order of Planck’s constant
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Heisenberg’s Uncertainty principle

The position and momentum of a particle cannot be

simultaneously measured with arbitrarily high precision.

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Heisenberg’s Uncertainty principle
Schrödinger formulated an equation that took account of wave–particle
duality and accounted for the motion of electrons in atoms.
To do so, he introduced the wavefunction , ψ (psi), a mathematical function
of the position coordinates x , y , and z which describes the behavior of an
electron.
The Schrödinger equation , of which the wavefunction is a
solution, for an electron free to move in one dimension is

where me is the mass of an electron, V is the potential energy of the electron,

and E is its total energy.

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The Schrödinger Equation

It describes the wave and particle properties of an electron in

terms of its position, mass, total energy and potential energy.

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Particle in a Box

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 The wave equation for locations within the box is

A general solution to describe the possible waves in the box would then be

Applying boundary conditions

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 Because both positive and negative values yield the same
results, substituting the positive value for r into the solution for
r gives

This expression may be solved for E :

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 Substituting r = np/a into the wave function gives

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Particle in a Box

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The Schrödinger Equation

• Solving the equation leads to wave functions.

• The wave function gives the shape of the electronic

orbital. [“Shape” really refers to density of electronic
charges.]

• The square of the wave function, gives the probability

of finding the electron ( electron density ).

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ORBITALS AND QUANTUM NUMBERS
Schrödinger’s equation requires 3 quantum numbers:
1. Principal Quantum Number, n. This is the same as Bohr’s n. As
n becomes larger, the atom becomes larger and the electron is
further from the nucleus. ( n = 1 , 2 , 3 , 4 , …. )
2. Angular Momentum Quantum Number, l. This quantum number
depends on the value of n. The values of l begin at 0 and
increase to (n - 1). We usually use letters for l (s, p, d and f for l =
0, 1, 2, and 3). Usually we refer to the s, p, d and f-orbitals.
3. Magnetic Quantum Number, ml. This quantum number depends
on l . The magnetic quantum number has integral values between
- l and + l . Magnetic quantum numbers give the 3D orientation of
each orbital.
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 ANGULAR WAVE FUNCTIONS:

- Determines how the probability changes from point to point at a given

distance from the center of the atom

- Gives the shape and orientation in space of the orbitals.

RADIAL WAVE FUNCTIONS

- Determined by quantum numbers n and l

- Radial probability function (squared) describes the probability of finding the

electron at a given distance from the nucleus

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KEY PRINCIPLES OF QUANTUM MECHANICS:

❖ Electrons can behave as particles or as waves

❖ Solutions to the Schrodinger equation gives wave functions

which describes the properties and location of the electron in
an an atom

❖ The square of the wave function gives the probability of

finding the electron in a given location.

❖ Schrodinger’s equations requires 3 quantum numbers (n, l,

ml)

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ATOMIC ORBITALS

Energy levels (Hydrogenic)

Shells, Subshells, and Orbitals

Electron Spin

Nodes

Radial Variation of atomic Orbitals

Radial Distribution Function

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ATOMIC ORBITALS – Energy Levels

The energy of the bound electron is determined by the

principal quantum number n, l specifies the magnitude of
the orbital angular momentum and ml
Each quantum number specifies a physical property of
the atomic orbital
n – size of the orbital (n increases becomes more
diffuse)
l - shape of the orbital (l increases # of lobes increases)
ml – orientation of the lobes

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 ATOMIC ORBITALS – shells, subshells, orbitals

In Hydrogen and hydrogen-like atoms, all orbitals of the same n belong

to the same shell, all with the same value of l belong to the same
subshell, and individual orbitals are distinguished by the ml value.

Shells with n = 1, 2, 3, 4….. Are commonly known as K, L, M, N.. Shells

Value of l 0 1 2 3 4 5
Subshell designation s p d f g h

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 ATOMIC ORBITALS – Electron Spins

The intrinsic spin angular momentum of an electron is defined by the

two quantum numbers s and ms. Four quantum numbers are needed
to define the state of an electron in a hydrogenic atom.

Because the spin state of an electron must be specified if the state of

the atom is to be specified fully, it is common to say that the state of an
electron in a hydrogenic atom is characterized by four quantum
numbers, namely n, l, ml, and ms (the fifth quantum number, s, is fixed
at 1/2)

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ATOMIC ORBITAL - NODAL SURFACES

Probability of finding an
electron = 0

=l

=n-l-1

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 SAMPLE PROBLEM:

How many nodes (radial + angular) nodes do 3p, 3d, and 4f orbitals
have?

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Atomic Structures Many Electron Atoms
‘many-electron atom’ is an atom with more than one electron.

The exact solution of the Schrodinger equation for an atom with N electrons would
be a function of the 3 N coordinates of all the electrons and would be extremely
challenging to find exact formulas for such complicated functions

Modern software can also generate graphical representations of the resulting

orbitals that can assist in the interpretation of the properties of the many
electron atom.

For most of inorganic chemistry we rely on the orbital approximation , in which

each electron occupies an atomic orbital that resembles those found in
hydrogenic atoms.

When we say that an electron ‘occupies’ an atomic orbital, we mean that it is

described by the corresponding wavefunction and set of quantum numbers.
ELECTRON CONFIGURATION:
❖ The ground-state electron configuration is a specification of the orbital occupation
of an atom in its lowest energy state.

❖ The exclusion principle forbids more than two electrons to occupy a single orbital.
(Pauli’s Exclusion Principle)

❖ The nuclear charge experienced by an electron is reduced by shielding by other

electrons.

❖ Trends in effective nuclear charge can be used to rationalize the trends in many
properties.

❖ As a result of the combined effects of penetration and shielding, the order of energy
levels in a shell of a many electron atom is s p d f.

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SHELDING AND
PENETRATION

The reduction of the true

nuclear charge to the effective
nuclear charge by the other
electrons is called shielding.

The presence of an electron

inside shells of other electrons
is called penetration

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 The electron at a radius r experiences a repulsion
from the total charge within the sphere of radius r ;
charge outside that radius has no net effect.

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Slater’s Rule:

Effective Nuclear Charge, Z* = Z – S

Z = nuclear charge, S = shielding constant

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 SHELDING AND PENETRATION

As a result of penetration and shielding, the order of

energies in many-electron atoms is typically

ns < np < nd < nf

because, in a given shell, s orbitals are the most

penetrating and f orbitals are the least penetrating.

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THE BUILDING UP PRINCIPLE: AUFBAU

1. Electrons are placed in orbitals to give the lowest total electronic

energy to the atom

2. Pauli’s Exclusion Principle. Each electron will have a unique set of

quantum numbers.

3. Hund’s Rule of maximum multiplicity. Electrons are to be placed in

orbitals to give the maximum total spin possible.

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 ELECTRON CONFIGURATION

spin multiplicity = # of unpaired electrons +1

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 Coulombic Energy and Exchange Energy

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Electron Configuration

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ELECTRON CONFIGURATION

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 STABILITY OF HALF- and FULLY FILLED ORBITALS

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STABILITY OF HALF- and FULLY FILLED ORBITALS

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SCHEMATIC ENERGY LEVELS FOR TRANSITION ELEMENTS

The effective nuclear

charge that an electron
experiences generally
increases as the most
probable distance of the
electrons from the
nucleus decreases

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SAMPLE PROBLEM

Write the condensed electron configuration for Iron (Z = 26)

What is the spin multiplicity in the valence subshell?

Dia- or paramagnetic?

Determine πc and πe
Condensed electron configuration for Fe+2 and Fe+3

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PERIODIC PROPERTIES OF THE ATOMS

IONIZATION ENERGY

ELECTRON AFFINITY

COVALENT AND IONIC RADII

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IONIZATION ENERGY

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IONIZATION ENERGY

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SAMPLE PROBLEM

The first four ionization energy of element X are 403, 2633, 3900, and 5080
kL/mol. To what periodic group does element X belong? Give reason/s for
your choice?

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ELECTRON AFFINITY

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 ATOMIC RADII

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 ATOMIC RADII

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 ATOMIC RADII and NUCLEAR CHARGE

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 Assignment 1

In Housecroft and Sharpe’s “Inorganic Chemistry”, 4th edition, answer

Problems 1.1, 1.12, 1.14, 1.25, and 1.26.

In Miessler and Tarr’s “Inorganic Chemistry”, 5th edition, answer

Problems 2.1, 2.2, 2.18, 2.23, and 2.29.

In Shriver and Atkin’s “Inorganic Chemistry”, 5th edition, answer

Problems 1.1, 1.11, 1.25, 1.27, and 1.28.

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