Atomic Structure

Dalton’s Atomic Theory and the Modern

view of Atomic Structure
 Early Ideas of Atoms – Democritus’ Theory
• The concept of the atom was first proposed about 2,500 years ago.
• It has always been difficult to convince people of the existence of things that are
too small to see.
• We will spend some time considering the evidence (observations) that convince
scientists of the existence of atoms.
Democritus
• Democritus (460-370 BC) and other early Greek philosophers thought that the
material world must be made up of tiny indivisible particles that they called
atomos, meaning "indivisible"
• Democritus then reasoned that changes occur when the many atomos in an
object were reconnected or recombined in different ways.
 Early Ideas of Atoms – Democritus’ Theory
• He even extended his theory, suggesting that there were different varieties of
atomos with different shapes, sizes, and masses.
• He thought, however, that shape, size and mass were the only properties
differentiating the different types of atomos.
• According to Democritus, other characteristics, like colour and taste, did not reflect
properties of the atomos themselves, but rather, resulted from the different ways
in which the atomos were combined and connected to one another.
• Democritus’ theories were scoffed at, and the "atomic" view of matter faded for
many centuries.
• The notion of atoms re-emerged in Europe during the seventeenth century, when
scientists tried to explain the properties of gases.
 Early Ideas of Atoms – Dalton’s Atomic
Theory
• As chemists learned to measure the amounts of elements that reacted with one
another to form new substances, the ground was laid for an atomic theory that
linked the idea of elements with the idea of atoms.
• That theory came from the work of an English school teacher, John Dalton during
the period from 1803-1807.
• Dalton's atomic theory involved the following postulates (or hypotheses).
 Early Ideas of Atoms – Dalton’s Atomic
Theory
• Dalton's theory explains several simple laws of chemical combination that were
known during his time. One of these laws was the law of constant composition:
In a given compound, the relative numbers and kinds of atoms are constant.
• This law is the basis of Dalton's Postulate 4.
• Another fundamental chemical law was the law of conservation of mass aka (also
known as) the law of conservation of matter:
The total mass of materials present after a chemical reaction is the same as the
total mass present before the reaction.
• This law is the basis for Postulate 3. Dalton proposed that atoms always retain their
identities and that atoms taking part in a chemical reaction rearrange to give new
chemical combinations.
 Early Ideas of Atoms – Dalton’s Atomic
Theory
• A good theory explains the known facts and predicts new ones. Dalton used his
theory to deduce the law of multiple proportions:
If two elements A and B combine to form more than one compound, the masses of
B that can combine with a given mass of A are in the ratio of small whole numbers.
 The Modern view of Atomic Structure
• Dalton reached his conclusion about atoms based on chemical observations in the
macroscopic world of the laboratory. Neither he nor those who followed him
during the century after his work was published had direct evidence for the
existence of atoms.
• Today’s world is a microscopic one where we can use powerful instruments to
measure the properties of individual atoms and even provide images of them.
• As scientists developed methods for more detailed studying of the nature of
matter, the atom, which was supposed to be indivisible, began to show signs of a
more complex structure.
• Before we summarize the current model of atomic structure, let us briefly
consider a few of the landmark discoveries (also referred to as models) along the
following timeline that led to that model.
The Modern view of Atomic Structure
 Discovery of the Electron
• In the mid-1800s, scientists were beginning to realize that the study of chemistry
and the study of electricity were actually related.
• First, a man named Michael Faraday showed how passing electricity through
mixtures of different chemicals could cause chemical reactions.
• Shortly after that, scientists found that by forcing electricity through a tube filled
with gas, the electricity made the gas glow!
• Scientists didn’t, however, understand the relationship between chemicals and
electricity until a British physicist named J. J. Thomson began experimenting with
what is known as a cathode ray tube.
• The following figures show a picture and a basic diagram of a cathode ray tube like
the one J. J. Thomson would have used. A cathode ray tube is a small glass tube
with a cathode (a negatively charged metal plate) and an anode (a positively
charged metal plate) at opposite ends.
Discovery of the Electron
 Discovery of the Electron
• By separating the cathode and anode by a short distance, the cathode ray tube can
generate what are known as cathode rays – rays of electricity that flow from the
cathode to the anode.
• J. J. Thomson wanted to know what cathode rays were, where cathode rays came
from, and whether cathode rays had any mass or charge.
• Through his rigorous experiments, J. J. Thomson suggested that the small, negatively
charged particles making up the cathode ray were actually pieces of atoms.
• He called these pieces “corpuscles,” although today we know them as electrons.
• Thanks to his clever experiments and careful reasoning, J. J. Thomson is credited with
the discovery of the electron.
• In 1897 J. J. Thomson (1856–1940) studied these negatively charged particles more
• carefully. By studying the degree of deflections of cathode rays in different electric and
magnetic fields, Thomson determined the ratio of the charge (e) of the electron to its
mass (m). The modern value for this ratio is
e/m = 1.75882 x 108 coulomb (C)/gram
 Discovery of the Electron
The oil drop apparatus

1916 – Robert Millikan

determines the mass of the
electron: 1/1840 the mass of a
hydrogen atom; has one unit of
negative charge

Mass of the electron is 9.11 x 10-28 g

 Discovery of the Electron
• With his oil drop experiment, Robert Millikan was able to accurately measure the
charge of the electron. When combined with the charge to mass ratio, he was able to
calculate the mass of the electron.

Millikan's oil-drop experiment. A

representation of the apparatus
Millikan used to measure the
charge of the electron.
 Thomson’s Plum Pudding Model
• When Thomson discovered the negative electron, he realized that atoms had to contain
positive material as well – otherwise they wouldn’t be neutral overall.
• As a result, Thomson formulated what’s known as the “plum pudding” model for the
atom.
• Thomson’s plum pudding model was much like a
chocolate chip cookie. Notice (on the next slide)
how the chocolate chips are the negatively
charged electrons, while the positive charge is
spread throughout the entire cookie.
• J.J. Thomson had measured the charge to mass
ratio of the electron, but had been unable to
accurately measure the charge on the electron.
A plum pudding in which the raisins
represent the distribution of
electrons in the atom.
 Rutherford’s Nuclear Model
• Everything about Thomson’s experiments suggested the “plum pudding” model was
correct – but according to the scientific method, any new theory or model should be
tested by further experimentation and observation.
• Disproving Thomson’s “plum pudding” model began with the discovery that an element
known as uranium emits positively charged particles called alpha particles as it
undergoes radioactive decay.
• Radioactivity is the spontaneous emission of radiation by an atom. It only happens with
a few very unstable elements.
• Alpha particles themselves didn’t prove anything about the structure of the atom, they
were, however, used to conduct some very interesting experiments.
• Rutherford found from his gold foil experiment that when he fired alpha particles at a
very thin piece of gold foil, an interesting thing happened. Almost all of the alpha
particles went straight through the foil as if they’d hit nothing at all. This was what he
expected to happen.
 Rutherford’s Nuclear Model
• Rutherford decided that the only way to explain his results was to assume that the
positive matter forming the gold atoms was not, in fact, distributed like the batter in
plum pudding, but rather, was concentrated in one spot, forming a small positively
charged particle somewhere in the centre of the gold atom.
• We now call this clump of positively charged mass the nucleus.
• According to Rutherford, the presence of a nucleus explained his experiments,
because it implied that most alpha particles passed through the gold foil without
hitting anything at all. Once in a while, though, the alpha particles would actually
collide with a gold nucleus, causing the alpha particles to be deflected, or even to
bounce right back in the direction they came from.
 Rutherford’s Nuclear Model

Rutherford postulated a very

small, dense nucleus with the
electrons around the outside of
the atom.
Most of the volume of the atom
is empty space.
 Rutherford’s Nuclear Model

If an atom could be
expanded to the size of a
football stadium, the
nucleus would be the
size of a single
blueberry.
 Rutherford’s Nuclear Model
• Subsequent experimental studies led to the discovery of both positive particles
(protons) and neutral particles (neutrons) in the nucleus. Protons were discovered
in 1919 by Rutherford. In 1932 British scientist James Chadwick (1891-1972)
discovered neutrons.
 Radioactivity
• In 1896 the French scientist Henri Becquerel (1852-1908) was studying a uranium
compound when he discovered that it spontaneously emits high-energy radiation.
• This spontaneous emission of radiation is called radioactivity.
• At Becquerel's suggestion Marie Curie and her husband, Pierre, began experiments to
isolate the radioactive components of the compound.
• Further study of the nature of radioactivity, principally by the British scientist Ernest
Rutherford, revealed three types of radiation:
alpha ( ), beta ( ), and gamma ( ) radiation.
• Each type differs in its response to an electric field, as shown in the following figure.
• The paths of both a and {3 radiation are bent by the electric field, although in
opposite directions; y radiation αis unaffected.
Radioactivity
 Radioactivity
• Rutherford showed that both  and  rays consist of fast-moving particles, which
were called  and  particles.
• In fact,  particles are high-speed electrons and can be considered the radioactive
equivalent of cathode rays. They are attracted to a positively charged plate.
• The  particles have a positive charge and are attracted toward a negative plate.
• In units of the charge of the electron,  particles have a charge of 1- and  particles a
charge of 2+.
• Each  particle has a mass about 7400 times that of an electron.
• Gamma radiation is high-energy radiation similar to X-rays; it does not consist of
particles and carries no charge
 The Bohr Model
• By 1913, the evolution of our concept of the atom had proceeded from Dalton’s
indivisible spheres idea to J. J. Thomson’s plum pudding model and then to
Rutherford’s nuclear atom theory.
• Rutherford, in addition to carrying out the brilliant experiment that demonstrated
the presence of the atomic nucleus, also proposed that the electrons circled the
nucleus in a planetary type motion.

• In 1913, the Danish physicist Niels Bohr

proposed a model of the electron
cloud of an atom in which electrons
orbit the nucleus and were able to
produce atomic spectrum.
 The Bohr Model
• Understanding Bohr’s model requires some knowledge of electromagnetic radiation
(or light).
• When gaseous atoms of a given element are heated, they emit light of only specific
energies. When gaseous atoms of that same element absorb light, they absorb
those same energies.
• To explain these phenomena of light emission and light absorption, Niels Bohr
(1885–1962) postulated that the electrons in atoms are arranged in orbits, each
with a definite energy.
• The Bohr theory was the first to include the explanation that electrons in atoms
have discrete energy levels; that is, electrons may be found only in orbits with
specific energies.
 The Bohr Model
Energy Levels
• Bohr’s key idea in his model of the atom is that electrons occupy definite orbits that
require the electron to have a specific amount of energy.
• In order for an electron to be in the electron cloud of an atom, it must be in one of
the allowable orbits and it must have the precise energy required for that orbit.
• Orbits closer to the nucleus would require smaller amounts of energy for an electron
and orbits farther from the nucleus would require the electrons to have a greater
amount of energy.
• The possible orbits are known as energy levels. One of the weaknesses of Bohr’s
model was that he could not offer a reason why only certain energy levels or orbits
were allowed.
 The Bohr Model
• Bohr hypothesized that the only way electrons could gain or lose energy would be to
move from one energy level to another, thus gaining or losing precise amounts of
energy. It would be like a ladder that had rungs at certain heights, as illustrated below.
• The only way you can be on that ladder is to be on one of the
rungs, and the only way you could move up or down is to
move to one of the other rungs.
• Other rules for the ladder are that only one person can be on
a given rung and that the ladder occupants must be on the
lowest rung available.
• Suppose we had such a ladder with 10 rungs. If the ladder had
five people on it, they would be on the lowest five rungs. In
this situation, no person could move down because all the
lower rungs are full.
 The Bohr Model
• Bohr worked out the rules for the maximum number of electrons that could be in
each energy level in his model.
• In its normal state (ground state), this would require the atom to have all of its
electrons in the lowest energy levels available.
• Under these circumstances, no electron could lose energy because no electron could
move down to a lower energy level.
• In this way, the Bohr model explained why electrons circling the nucleus did not emit
energy and spiral into the nucleus.
Bohr’s Model and Atomic Spectra
• The evidence used to support Bohr’s model came from the atomic spectra.
He suggested that an atomic spectrum is made by the electrons in an atom moving
energy levels.
• The electrons typically have the lowest energy possible, called ground state.
 The Bohr Model
• If electrons are given energy (through heat, electricity, light, etc.), these electrons in
an atom could absorb the energy by jumping to a higher energy level or an excited
state.
• The electrons then give off the energy in the form of a piece of light, called a photon,
they had absorbed to fall back to a lower energy level.
• The energy emitted by electrons dropping back to lower energy levels would always
be precise amounts of energy because the differences in energy levels were precise.
• This explains why we see specific lines of light when looking at an atomic spectrum –
each line of light matches a specific "step down" that an electron can take in that
atom.
• This also explains why each element produces a different atomic spectrum. Because
each element has different acceptable energy levels for their electrons, the possible
steps each element’s electrons can take differ from all other elements.
 The Bohr Model
• The flames in the picture below represent (left to right) potassium, copper, cesium,
boron, and calcium.
• Each element has a characteristic spectrum from the emission of light from hot atoms;
therefore, these spectra can be used to identify elements.
• Our current understanding of the electronic structure of the atom started with the
discovery and explanation of
the spectra produced in hot
gases and flames.
The Bohr Model
 The Bohr Model
ENERGY CONSERVATION AND SPECTRAL LINES
• An electron in an excited state normally returns very quickly to its ground state, either
directly or via an intermediate state.
• When the electron moves from its initial Ei to its final Ef state, a photon is emitted (or
absorbed, if Ei < Ef).
• The energy of the photon emitted (or absorbed) is given by energy conservation:

For hydrogen:
 The Bohr Model
• To explain the hydrogen spectrum shown below, Bohr suggested that in each
hydrogen atom, the electron revolves about the nucleus in one of several possible
circular orbits, each having a definite radius corresponding to a definite energy for
the electron.
• An electron in the orbit closest to the nucleus has the lowest energy. With the
electron in that orbit, the atom is said to be in its lowest energy state, or ground
state.
• If a discrete quantity of additional energy were absorbed by the atom in some
manner, the electron might be able to move into another orbit having a higher
energy.
• The hydrogen atom would then be in an excited state. An atom in the excited
state will return to the ground state and give off its excess energy as light in the
process.
 The Bohr Model
• In returning to the ground state, the energy may be emitted all at once, or it may be
emitted in a stepwise manner (but not continuously) as the electron drops from a
higher allowed orbit to allowed orbits of lower and lower energy.
• Since each orbit corresponds to a definite energy level, the energy of the light
emitted will correspond to the definite differences in energy between levels.
• Therefore, the light emitted as the atom returns to its ground state will have a
definite energy or a definite set of energies as shown below.
• The discrete amounts of energy emitted or absorbed by an atom or molecule are
called quanta (singular, quantum). A quantum of light energy is called a photon.
 Atomic Numbers, Mass Numbers, and
Isotopes
• What makes an atom of one element different from an atom of another element? For
example, how does an atom of carbon differ from an atom of oxygen?
• The significant difference is in their subatomic compositions. The atoms of each
element have a characteristic number of protons.

Subatomic Particles
• Every atom has nearly all of its mass concentrated in a tiny region in the centre of the
atom called the nucleus.
• The nucleus is made up of particles called nucleons. There are two types of nucleon:
protons and neutrons.
• Atoms of different elements have different numbers of protons.
• Outside the nucleus, particles called electrons move around in regions of space called
orbitals.
 Atomic Numbers, Mass Numbers, and
Isotopes
Numbers of nucleons
Proton number and nucleon number
• The number of protons in the nucleus of an atom is called the proton number (Z). It
is also known as the atomic number.
• Every atom of the same element has the same number of protons in its nucleus. It is
the proton number that makes an atom what it is. For example, an atom with a
proton number of 11 must be an atom of the element sodium.
• The Periodic Table of elements is arranged in order of the proton numbers of the
individual elements.
• The nucleon number (A) is the number of protons plus neutrons in the nucleus of an
atom. This is also known as the mass number.
 Atomic Numbers, Mass Numbers, and
Isotopes
How many neutrons?
• We can use the nucleon number and proton number to find the number of neutrons
in an atom. As:
nucleon number = number of protons + number of neutrons
• Then:
number of neutrons = nucleon number – number of protons
=A–Z
• For example, an atom of aluminium has a nucleon number of 27 and a proton
number of 13. So an aluminium atom has 27 – 13 = 14 neutrons.
 Atomic Numbers, Mass Numbers, and
Isotopes
Isotopes
• All atoms of the same element have the same number of protons. However, they
may have different numbers of neutrons.
• Atoms of the same element that have differing numbers of neutrons are called
isotopes.

• Isotopes of a particular element have the same chemical properties because they
have the same number of electrons.
• They have slightly different physical properties, such as small differences in density.
• We can write symbols for isotopes. We write the nucleon number at the top left of
the chemical symbol and the proton number at the bottom left.
 Atomic Numbers, Mass Numbers, and
Isotopes
• The symbol for the isotope of boron with 5 protons and 11 nucleons is written:

• Hydrogen has three isotopes. The atomic structure and isotopic symbols for the three
isotopes of hydrogen are shown below:
 Atomic Numbers, Mass Numbers, and
Isotopes
• When writing generally about isotopes, chemists also name them by omitting the
proton number and placing the nucleon number after the name. For example, the
isotopes of hydrogen can be called hydrogen-1, hydrogen-2 and hydrogen-3.
• Isotopes can be radioactive or non-radioactive. Specific radioisotopes (radioactive
isotopes) can be used to check for leaks in oil or gas pipelines and to check the
thickness of paper. They are also used in medicine to treat some types of cancer and
to check the activity of the thyroid gland in the throat.
Atomic Mass
• Because each proton and each neutron contribute approximately one amu to the
mass of an atom, and each electron contributes far less, the atomic mass of a single
atom is approximately equal to its mass number (a whole number).
• However, the average masses of atoms of most elements are not whole numbers
because most elements exist naturally as mixtures of two or more isotopes.
 Atomic Numbers, Mass Numbers, and
Isotopes
• The mass of an element shown in a periodic table or listed in a table of atomic masses
is a weighted, average mass of all the isotopes present in a naturally occurring sample
of that element.
• This is equal to the sum of each individual isotope’s mass multiplied by its fractional
abundance.

• For example, the element boron is composed of two isotopes: About 19.9% of all
boron atoms are 10B with a mass of 10.0129 amu, and the remaining 80.1% are 11B
with a mass of 11.0093 amu.
• The average atomic mass for boron is calculated to be:
boron average mass = (0.199 × 10.0129 amu) + (0.801 × 11.0093 amu)
= 1.99 amu + 8.82 amu
= 10.81 amu
 Atomic Numbers, Mass Numbers, and
Isotopes
• It is important to understand that no single boron atom weighs exactly 10.8 amu;
10.8 amu is the average mass of all boron atoms, and individual boron atoms weigh
either approximately 10 amu or 11 amu.
Example 2:
 Atomic Numbers, Mass Numbers, and
Isotopes
Exercise:

• We can also do variations of this type of calculation, as shown in the next example.
 Atomic Numbers, Mass Numbers, and
Isotopes
• The occurrence and natural abundances of isotopes can be experimentally
determined using an instrument called a mass spectrometer.
• Mass spectrometry (MS) is widely used in chemistry, forensics, medicine,
environmental science, and many other fields to analyze and help identify the
substances in a sample of material.
• In a typical mass spectrometer (shown below), the sample is vaporized and exposed
to a high-energy electron beam that causes the sample’s atoms (or molecules) to
become electrically charged, typically by losing one or more electrons.
• These cations then pass through a (variable) electric or magnetic field that deflects
each cation’s path to an extent that depends on both its mass and charge (similar to
how the path of a large steel ball bearing rolling past a magnet is deflected to a lesser
extent that that of a small steel ball bearing).
 Isotopes
• The figure below illustrates an analysis of zirconium (Zr) in a mass spectrometer
which produces a mass spectrum with peaks showing the different isotopes of Zr.
 Isotopes
• The ions are detected, and a plot of the relative number of ions generated versus
their mass-to-charge ratios (a mass spectrum) is made.
• The height of each vertical feature or peak in a mass spectrum is proportional to the
fraction of cations with the specified mass-to-charge ratio.
• Since its initial use during the development of modern atomic theory, MS has evolved
to become a powerful tool for chemical analysis in a wide range of applications.

A mass spectrometer is a large and complex

instrument. A mass spectrometer can be
used to measure the mass of each isotope
present in an element. It also compares
how much of each isotope is present – the
relative abundance (isotopic abundance).
 The Quantum Mechanical Model of the
Atom
• By the mid-1920s it had become apparent that the Bohr model could not be used to
explain much of the observed phenomena about electronic structure of atoms.
• A totally new approach was needed. Three physicists were at the forefront of this
effort: Werner Heisenberg (1901–1976), Louis de Broglie (1892–1987), and Erwin
Schrödinger (1887–1961).
• de Broglie originated the idea that the electron, previously considered to be a
particle, also shows wave properties.
• In 1926 the Austrian physicist Erwin Schródinger proposed an equation, now known
as Schródinger's wave equation, that incorporates both the wavelike behaviour and
the particle-like behaviour of the electron. His work opened a new way of dealing
with subatomic particles, known as either quantum mechanics or wave mechanics.
 The Quantum Mechanical Model of the
Atom
• The application of Schródinger 's equation requires advanced calculus, and we will
not be concerned with the details of his approach. We will, however, qualitatively
consider the results he obtained, because they give us a powerful new way to view
electronic structure.
• Let's begin by examining the electronic structure of the simplest atom, hydrogen.
• In the same way that a plucked guitar string vibrates as a standing wave, Schrodinger
treated the electron as a standing circular wave around the nucleus.
 The Quantum Mechanical Model of the
Atom
• The dots in this figure indicate the nodes, or points of
zero lateral (sideways) displacement, for a given
wave.
• Note that there are limitations on the allowed
wavelengths of the standing wave.
• Each end of the string is fixed, so there is always a
node at each end.
• This means that there must be a whole number of
half wavelengths in any of the allowed motions of the
string
 The Quantum Mechanical Model of the
Atom

• The hydrogen electron visualized as a standing wave around the

nucleus.
• The circumference of a particular circular orbit would have to
correspond to a whole number of wavelengths, as shown in (a)
and (b), or else destructive interference occurs, as shown in (c).
• This is consistent with the fact that only certain electron energies
are allowed; the atom is quantized.
 The Quantum Mechanical Model of the
Atom
• Solving Schrodinger's equation leads to a series of mathematical functions called
wave functions that describe the electron in an atom. These wave functions are
usually represented by the symbol Ψ (the lowercase Greek letter psi).
• AIthough the wave function itself has no direct physical meaning, the square of the
wave function, Ψ2, provides information about an electron's location when the
electron is in an allowed energy state.
• For the hydrogen atom, the allowed energies are the same as those predicted by the
Bohr model. However, the Bohr model assumes that the electron is in a circular orbit
of some particular radius about the nucleus. In the quantum mechanical model, the
electron's location cannot be described so simply.
• According to the Heisenberg’s uncertainty principle, if we know the momentum of
the electron with high accuracy, our simultaneous knowledge of its location is very
uncertain.
 The Quantum Mechanical Model of the
Atom
• Thus, we cannot hope to specify the exact location of an individual electron around
the nucleus. Rather, we must be content with a kind of statistical knowledge.
• In the quantum mechanical model, we therefore speak of the probability that the
electron will be in a certain region of space at a given instant.
• As it turns out, the square of the wave function, Ψ2, at a given point in space
represents the probability that the electron will be found at that location.
• For this reason, Ψ2 is called either the probability density or the electron density.
Electron-density distribution. This figure represents the
probability of where in the space surrounding the nucleus the
electron is to be found in a hydrogen atom in its ground
state. The regions with a high density of dots correspond to
relatively large values for Ψ2 and are therefore regions where
there is a high probability of finding the electron.
 The Quantum Mechanical Model of the
Atom
Orbitals and Quantum Numbers
• The solution to Schrodinger's equation for the hydrogen atom yields a set of wave
functions and corresponding energies. These wave functions are called orbitals.
• Each orbital describes a specific distribution of electron density in space, as given by
the orbital' s probability density.
• Each orbital, therefore, has a characteristic energy and shape. For example, the
lowest-energy orbital in the hydrogen atom has the shape illustrated in the figure
shown above.
• Note that an orbital (in the quantum mechanical model) is not the same as an orbit
(in the Bohr model). The quantum mechanical model does not refer to orbits,
because the motion of the electron in an atom cannot be precisely measured or
tracked (Heisenberg uncertainty principle).
 The Quantum Mechanical Model of the
Atom
Orbitals and Quantum Numbers
• The Bohr model introduced a single quantum number, n, to describe an orbit. The
quantum mechanical model uses three quantum numbers, n, l, and ml, which result
naturally from the mathematics used, to describe an orbital.
• Let’s consider what information we obtain from each of these quantum numbers and
how they are interrelated.
1. The principal quantum number, n, can have positive integral values of 1, 2, 3,
and so forth. As n increases, the orbital becomes larger, and the electron
spends more time farther from the nucleus. An increase in n also means that
the electron has a higher energy and is therefore less tightly bound to the
nucleus.
 The Quantum Mechanical Model of the
Atom
Orbitals and Quantum Numbers
2. The second quantum number – the azimuthal or angular momentum
quantum number, l – can have integral values from 0 to (n - 1) for each value
of n. This quantum number defines the shape of the orbital. The value of l for
a particular orbital is generally designated the letters s, p, d, and f
corresponding to l values of 0,1,2, and 3, respectively, as summarized here:

[The letters s, p, d, and f come from the words sharp, principal, diffuse, and
fundamental, which were used to describe certain features of spectra before
quantum mechanics was developed]
 The Quantum Mechanical Model of the
Atom
Orbitals and Quantum Numbers
3. The magnetic quantum number, ml, can have integral values between -n
and n, including zero. This quantum number describes the orientation of
the orbital in space.
• The collection of orbitals with the same value of n is called an electron shell. All the
orbitals that have n = 3, for example, are said to be in the third shell.
• Further, the set of orbitals that have the same n and l values is called a subshell.
• Each subshell is designated by a number (the value of n) and a letter (s, p, d, or f,
corresponding to the value of l).
• For example, the orbitals that have n = 3 and l = 2 are called 3d orbitals and are in
the 3d subshell.
• The following table shows the relationship among Values of n, l, and ml . It
summarizes the possible values of the quantum numbers l, and ml for values of n
through n = 4.
The Quantum Mechanical Model of the
Atom
 The Quantum Mechanical Model of the
Atom
• The restrictions on the possible values of the quantum numbers give rise
to the following very important observations:
1. The shell with principal quantum number n will consist of
exactly n subshells. Each subshell corresponds to a different
allowed value of l from 0 to (n - 1). Thus, the first shell (n = 1)
consists of only one subshell, the 1s (l = 0); the second shell
(n = 2) consists of two subshells, the 2s (l = 0) and 2p (l = 1); the
third shell consists of three subshells, 3s, 3p, and 3d, and so forth.
 The Quantum Mechanical Model of the
Atom
2. Each subshell consists of a specific number of orbitals. Each orbital
corresponds to a different allowed value of ml . For a given value of l, there are
(2l + 1) allowed values of ml, ranging from -l to +l. Thus, each s (l = 0) subshell
consists of one orbital, each p (l = 1) subshell consists of three orbitals, each d
(l = 2) subshell consists of five orbitals, and so forth.
3. The total number of orbitals in a shell is n2, where n is the principal quantum
number of the shell. The resulting number of orbitals for the shells – l, 4, 9, 16
– is related to a pattern seen in the periodic table: We see that the number of
elements in the rows of the periodic table – 2, 8, 18, and 32 – equals twice
these numbers.
• The adjacent diagram shows the relative
energies of the hydrogen atom orbitals through n
= 3. Each box represents an orbital; orbitals of
the same subshell, such as the 2p, are grouped
together.

Orbital energy levels In the hydrogen

atom. Each box represents an orbital.
Note that all orbitals with the same
value for the principal quantum number,
n, have the same energy.
 The Quantum Mechanical Model of the
Atom
• When the hydrogen electron occupies the lowest energy orbital (1s), the hydrogen
atom is said to be in its ground state. When the electron occupies any other orbital,
the atom is in an excited state.
• At ordinary temperatures, essentially all hydrogen atoms are in the ground state. The
electron can be excited to a higher-energy orbital by absorption of a photon of
appropriate energy.
 The Quantum Mechanical Model of the
Atom
Orbital Representation
• In our discussion of orbitals so far, we have emphasized their energies. But the
wave function also provides information about the electron's location in space
when it occupies an orbital.
• Let’s examine the ways that we can picture the orbitals. In doing so, we will examine
some important aspects of the electron-density distributions of the orbitals.
The s Orbitals
• One representation of the lowest-energy orbital of the hydrogen atom, the 1s, is
shown below.
• This type of drawing, which shows the distribution of electron density around the
nucleus, is one of the several ways we use to help us visualize orbitals.
• The first thing that we notice about the electron density for the 1s orbital is that it is
spherically symmetric – i.e., the electron density at a given distance from the nucleus
is the same regardless of the direction in which we proceed from the nucleus.
 The Quantum Mechanical Model of the
Atom
• All of the other s orbitals (2s, 3s, 4s, and so forth) are spherically symmetric as well.
• Remember that the l quantum number for the s orbitals is 0; therefore the ml
quantum number must be 0. Therefore, for each value of n, there is only one s orbital.
 The Quantum Mechanical Model of the
Atom
The p Orbitals
• The distribution of electron density for a 2p orbital is shown below.
• As we can see from this figure, the electron density is not distributed in a spherically
symmetric fashion as in an s orbital.
 The Quantum Mechanical Model of the
Atom
The p Orbitals
• Instead, the electron density is concentrated in two regions on either side of the
nucleus, separated by a node at the nucleus.
• We say that this dumbbell-shaped orbital has two Iobes.
• Remember that we are making no statement of how the electron is moving within the
orbital. The only thing Figure (a) portrays is the averaged distribution of the electron
density in a 2p orbital.
• Beginning with the n = 2 shell, each shell has three p orbitals.
• Recall that the I quantum number for p orbitals is 1. Therefore, the magnetic
quantum number ml can have three possible values: -1, 0, and +1. Thus, there are
three 2p orbitals, three 3p orbitals, and so forth, corresponding to the three possible
values of ml.
• Each set of p orbitals has the dumbbell shapes shown in Figure (a) above for the 2p
orbitals.
 The Quantum Mechanical Model of the
Atom
The p Orbitals
• For each value of n, the three p orbitals have the same size and shape but differ from
one another in spatial orientation.
• We usually represent p orbitals by drawing the shape and orientation of their wave
functions, as shown in Figure (b) above.
• lt is convenient to label these as the px, py and pz orbitals. The letter subscript
indicates the Cartesian axis along which the orbital is oriented.
• Like s orbitals, p orbitals increase in size as we move from 2p to 3p to 4p, and so forth.
The d and f Orbitals
• When n is 3 or greater, we encounter the d orbitals (for which l = 2).
• There are five 3d orbitals, five 4d orbitals, and so forth because in each shell there are
five possible values for the ml quantum number: - 2, - 1, 0, 1, and 2.
• The different d orbitals in a given shell have different shapes and orientations
in space, as shown below.
 The Quantum Mechanical Model of the
Atom
• When n is 4 or greater, there are seven equivalent f orbitals (for which 1 = 3).
• The shapes of the f orbitals are even more complicated than those of the d orbitals
and are not presented here.
• You must, nonetheless, be aware of f orbitals as we consider the electronic structure
of atoms in the lower part of the Periodic Table.
MULTI-ELECTRON ATOMS
• So far, we have seen that quantum mechanics leads to a very elegant description of
the hydrogen atom. This atom, however, has only one electron.
• How must our description of the electronic structure of atoms change when we
consider atoms with two or more electrons (a multi-electron atom)?
• To describe these atoms, we must consider the nature of orbitals and their relative
energies as well as how the electrons populate the available orbitals.
 The Quantum Mechanical Model of the
Atom
Orbitals and Their Energies
• The quantum mechanical model would not be very useful if we cannot extend what
we have leamed about hydrogen to other atoms.
• Fortunately, we can describe the electronic structure of a many-electron atom in
terms of orbitals like those of the hydrogen atom. Thus, we can continue to designate
orbitals as Is, 2px, and so forth. Further, these orbitals have the same general shapes
as the corresponding hydrogen orbitals.
• Although the shapes of the orbitals for many-electron atoms are the same as those
for hydrogen, the presence of more than one electron greatly changes the energies
of the orbitals.
• In hydrogen the energy of an orbital depends only on its principal quantum number,
n; the 3s, 3p, and 3d subshells all have the same energy, for instance.
• In a many-electron atom, however, the electron-electron repulsions cause the
different subshells to be at different energies, as shown in the figure below.
 The Quantum Mechanical Model of the
Atom
• To understand why this is so, we must consider the forces between the electrons and
how these forces are affected by the shapes of the orbitals.
• In a many-electron atom, for a given value of n, the energy of an orbital increases
with increasing value of l.
• We can see this illustrated in the figure above. Notice, for example, that the n = 3
orbitals (red) increase in energy in the order 3s < 3p < 3d.
• The figure above is a qualitative energy Ievel diagram; the exact energies of the
orbitals and their spacings differ from one atom to another.
• Notice that all orbitals of a given subshell (such as the five 3d orbitals) still have the
same energy as one another, just as they do in the hydrogen atom.
• Orbitals with the same energy are said to be degenerate.
 The Quantum Mechanical Model of the
Atom
Electron Spin and the Pauli Exclusion Principle
• We have now seen that we can use hydrogen-like orbitals to describe many-electron
atoms.
• What, however, determines which orbitals the electrons reside in? That is, how do
the electrons of a many-electron atom populate the available orbitals?
• To answer this question, we must consider an additional property of the electron.
• When scientists studied the line spectra of many-electron atoms in great detail, they
noticed a very puzzling feature: Lines that were originally thought to
be single were actually closely spaced pairs.
• This meant, in essence, that there were twice as many energy levels as there were
"supposed" to be.
• In 1925 the Dutch physicists George Uhlenbeck and Samuel Goudsmit proposed a
solution to this dilemma.
 The Quantum Mechanical Model of the
Atom
• They postulated that electrons have an intrinsic property, called electron spin, that
causes each electron to behave as if it were a tiny sphere spinning on its own axis.
• This observation led to the assignment of a new quantum number for the electron, in
addition to n, l, and ml, which we have already discussed.
• This new quantum number, the spin magnetic quantum number, is denoted ms (the
subscript s stands for spin).
• Two possible values are allowed for ms, +½ or -½ which was first interpreted as
indicating the two opposite directions in which the electron can spin.
 The Quantum Mechanical Model of the
Atom
• spinning charge produces a magnetic field.
• The two opposite directions of spin therefore produce oppositely directed magnetic
fields, as shown in in the figure above.
• These two opposite magnetic fields lead to the splitting of spectral lines into closely
spaced pairs.
• Electron spin is crucial for understanding the electronic structures of atoms.
• In 1925 the Austrian-born physicist Wolfgang Pauli (1900-1958) discovered the
principle that governs the arrangements of electrons in many-electron atoms.
• The Pauli exclusion principle states that no two electrons in an atom can have the
same set of four quantum numbers n, l, ml and ms.
• For a given orbital (Is, 2pz, and so forth), the values of n, l, and ml are fixed. Thus, if
we want to put more than one electron in an orbital and satisfy the Pauli exclusion
principIe, our only choice is to assign different ms values to the electrons.
 The Quantum Mechanical Model of the
Atom
• Because there are only two such values, we conclude that an orbital can hold a
maximum of two electrons and they must have opposite spins.
• This restriction allows us to index the electrons in an atom, giving their quantum
numbers and thereby defining the region in space where each electron is most likely
to be found. It also provides the key to one of the great problems in chemistry-
understanding the structure of the periodic table of the elements.

ELECTRON CONFIGURATIONS