1 - Atomic Structure - Rashed

Chemistry: The Central Science
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Erwin
Schrödinger
wave
mechanical
model
(1926)
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http://ffden-2.phys.uaf.edu/webproj/212_spring_2017/Nikolay_Donets/Nikolay_Donets/Slide3.htm
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http://ffden-2.phys.uaf.edu/webproj/212_spring_2017/Nikolay_Donets/Nikolay_Donets/Slide3.htm
Democritus Concept of Atom
Is matter continuous or discontinuous? Can you break a matter as long as you want?
Would you reach some ultimate particle beyond which further division is impossible?
To answer these questions, atomic theory developed. The concept of an atom is

originated from Greek philosopher Democritus.
Democritus studied the nature of matter and the constituents of all the substances.
He postulated that all matter consists of very small, indivisible particles, which he
named atomos (meaning uncuttable or indivisible).
Ancient Concepts of Atomic Structure
Dalton’s Atomic Theory
An English scientist John Dalton formulated a precise definition of the
indivisible building blocks of matter that we call atoms. He is called the
“Father of Modern Chemistry”. Dalton's theory of atoms relies on four basic
ideas:
 All 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 formed by the joining of atoms of two or more elements. In any compound, atoms combined
only in small whole-number ratios, such as 1:1, 1:2, 2:1, 2:3, to form compounds. H2O, CO2, CH4 etc…….
 Chemical reaction involves only the separation, combination, or rearrangement of atoms; it does not result in
their creation or destruction
Dalton’s Atomic Theory
(a) According to Dalton’s atomic theory, atoms of the same element are identical, but atoms of one
element are different from atoms of other elements. (b) Compound formed from atoms of elements X
and Y. In this case, the ratio of the atoms of element X to the atoms of element Y is 2:1. Note that a
chemical reaction results only in the rearrangement of atoms, not in their destruction or creation.
Discovery of Electron
 J. J. Thomson used a cathode ray tube and
his knowledge of electromagnetic theory
to determine the ratio of electric charge
to the mass of an individual electron.
 Cathode ray tube is a glass tube from
which most of the air has been evacuated.
When the two metal plates are connected to a high-voltage source, the negatively charged plate,
called the cathode, emits an invisible ray. The cathode ray is drawn to the positively charged plate,
called the anode, where it passes through a hole and continues traveling to the other end of the
tube. When the ray strikes the specially coated surface, it produces a strong fluorescence, or bright
light.
In some experiments, two electrically charged
plates and a magnet were added to the
outside of the cathode ray tube. The symbols
N and S denote the north and south poles of
the magnet. The cathode rays will strike the
end of the tube at A in the presence of a
magnetic field, at C in the presence of an
electric field, and at B when there are no
external fields present or when the effects of
the electric field and magnetic field cancel
each other.
Because the cathode ray is attracted by the plate bearing positive charges and repelled
by the plate bearing negative charges, it must consist of negatively charged particles.
 Thomson showed that the characteristics of cathode rays are independent of the
material making up the cathode. From such evidence, he concluded that a
cathode ray consists of a beam of negatively charged particles (electrons) and that
electrons are constituents of all matter. This means that atoms can be divided into
smaller substance
 He calculated the ratio of the electric charge (e) to its electron’s mass (me), which
is -1.76 X 108 C/g. He could not obtain either charge or the mass
Thomson proposed that an atom could be thought of as

a uniform, positive sphere of matter in which electrons
are embedded like raisins in a cake. This is called plum
pudding model
Determination of charge and mass
 In 1909, US physicist Robert Millikan performed a series of experiments and
succeeded in measuring the charge of the electron with great precision. His work
proved that the charge on each electron was exactly the same (1.602 X 10-19 C)
 Using this charge value in charge to mass ratio formula, he calculated mass of
electron, which is 9.109 X 10-28 g
 This mass is more than 1800 times smaller than the mass of the lightest atom
hydrogen (1.67 X 10-24 g). This clearly shows that electron is a subatomic particle.
Rutherford’s Nuclear Model of Atom
Ernest Rutherford studied the effects of bombarding
thin gold foil and other metal foils with alpha particles
(positively charged) from a radioactive source such as
uranium.
Rutherford's experiments provided him with two important
pieces of information:
First, most of the alpha particles traveled right through the

foil without being deflected at all. This means that atoms
consist mostly of empty space.
Second, a few of the alpha particles (about 1 in 8000) were deflected at very sharp angles. In
fact, some reflected completely backwards and were detected next to the gun from which they
were first produced. This reveals that the positive charge in an atom must all be packed
together in one small region of the atom. He called that region the nucleus of the atom. The
positively charged particles in the nucleus are called protons.
 In separate experiments, it was found that each proton carries the same quantity of
charge as an electron and has a mass of 1.67262 X 10-24 g : about 1840 times the mass
of the oppositely charged electron.
 At this stage of investigation, scientists perceived the atom as follows: The mass of a
nucleus constitutes most of the mass of the entire atom, but the nucleus occupies only
about 1/1013 of the volume of the atom.
 A typical atomic radius is about 100 pm, whereas the radius of

an atomic nucleus is only about 5 X 10-3 pm.
 Although the protons are confined to the nucleus of the atom,

the electrons are conceived of as being spread out about the
nucleus at some distance from it.
Problems with Rutherford’s Atomic Model
One part of Rutherford's model—the nucleus—has turned out to be correct. However, his
placement of electrons created some problems, which he himself recognized.
 The peculiar difficulty is that electrons cannot remain stationary in an atom. If they were
stationary, they would be attracted to the nucleus and become part of it.
 But the electrons could not be spinning around the nucleus either.
According to a well-known law of physics, charged particles (like
electrons) that travel through space give off energy. Moving electrons
would eventually lose energy, lose speed, and fall into the nucleus.
Electrons in Rutherford's atom could neither be at rest nor in motion.
Therefore, this model is unstable
Discovery of Neutron
 Rutherford’s model of atomic structure left one major problem unsolved. It was known that
hydrogen, the simplest atom, contains only one proton and that the helium atom contains
two protons. Therefore, the ratio of the mass of a helium atom to that of a hydrogen atom
should be 2:1. (Because electrons are much lighter than protons, their contribution to atomic
mass can be ignored.)
 In reality, however, the ratio is 4:1. Rutherford and others postulated that there must be
another type of subatomic particle in the atomic nucleus.
The proof was provided by another English physicist, James Chadwick in 1932
Discovery of Neutron
When Chadwick bombarded a thin sheet of beryllium with α particles, a very high-energy
radiation similar to γ rays was emitted by the metal. Later experiments showed that the rays
actually consisted of a third type of subatomic particles, which Chadwick named neutrons,
because they proved to be electrically neutral particles having a mass slightly greater than that of
protons.
The mystery of the mass ratio could now be explained. In the helium nucleus there are two
protons and two neutrons, but in the hydrogen nucleus there is only one proton and no
neutrons; therefore, the ratio is 4:1.
 An atom consists of a nucleus many times smaller than the atom itself, with
electrons occupying the remaining space.
 How are the electrons distributed in this space?
 What is the role of electrons in atomic stability, chemical bond formation?

 How many electrons are present in an atom?
 What energies do individual electrons possess?
Modern Theory of the Atom
 Atoms are composed of three main subatomic particles: electron, proton and neutron
 Most of the mass of the atom is concentrated in the nucleus of the atom
 The protons and neutrons are located within the nucleus, while the electrons exist outside
of the nucleus
 In stable atoms, the number of protons is equal to the number of electrons

Cont…
 The type of atom is determined by the number of protons it has
 The number of protons in an atom is equal to the atomic number
 The sum of the number of protons and neutrons in a particular atom is

called the atomic mass
 Valence electrons are the outermost electrons

Developments leading to the Bohr’s model of atom
• Results observed from the studies of interactions of radiations with matter have
provided immense information regarding the structure of atoms and molecules.
• Neil's Bohr utilized these results to improve upon the model proposed by
Rutherford.
Two developments played a major role in the formulation of Bohr’s model of atom.
1) Dual character of the electromagnetic radiation which means that

radiations possess both wave like and particle like properties, and
2) Experimental results regarding atomic spectra which can be explained
only by assuming quantized electronic energy levels in atoms.
From Classical Physics to Quantum Theory
The new era in physics started in 1900 with a young German physicist named Max Planck.
While analyzing the data on radiation emitted by solids heated to various temperatures, Planck discovered
that atoms and molecules emit energy only in certain discrete quantities, or quanta.
Physicists had always assumed that energy is continuous (any value of energy can be measured but for such
systems as the electrons in atoms which are stable only certain energies are permitted. The permitted
energies are discrete, not continuous) and that any amount of energy could be released in a radiation
process.
Planck’s quantum theory turned physics upside down. Indeed, the flurry of research that ensued altered our
concept of nature forever.
Properties of Waves
A wave is a continuously repeating change or oscillations in matter or
in a physical field by which energy is transmitted. For example, water
waves.
A wave can be characterized by it’s wavelength, height and

frequency. Wavelength (λ) is the distance between identical points
on successive waves. The frequency (ν) is the number of waves
that pass through a particular point in 1 second. Amplitude is
the vertical distance from the midline of a wave to the peak or
trough. The regular variation of the peaks and troughs enable us to
sense the propagation of the waves.
Properties of Waves
Another important property of waves is their speed, which depends on the type of wave
and the nature of the medium through which the wave is traveling (for example, air, water,
or a vacuum). The speed ( u ) of a wave is the product of its wavelength and its frequency:
Wavelength is usually expressed in units of meters, centimeters, or nanometers, and

frequency is measured in hertz (Hz) or s-1
The speed of the light wave in vacuum is a constant and independent of wavelength or
frequency. The speed is 3 X 108 m/s
Electromagnetic Radiation
 Electromagnetic radiation is the emission and transmission of
energy in the form of electromagnetic waves.
 According to James Clerk Maxwell’s theory, an electromagnetic
wave has an electric field component and a magnetic field
component. These two components have the same wavelength
and frequency, and hence the same speed, but they travel in
mutually perpendicular planes.
 This model accurately describes how energy in the form of
radiation can be propagated through space as vibrating electric
and magnetic fields.
Various Types of Electromagnetic Radiation
The three mysteries of 19th century
3. Line spectra of atoms with the special reference to hydrogen

Observation: Black body radiation
temperature
Attempts that applied the classical wave model to explain the relationship between the
energy given off by a hot object and the wavelength of the emitted radiation failed.
Planck’s Quantum Theory
 When solids are heated, they emit electromagnetic radiation over a wide range of
wavelengths.
 In 1900, Max Planck found a theoretical formula that exactly describes the intensity of light
of various frequencies emitted by a hot solid at different temperatures.
 Classical physics assumed that atoms and molecules could emit (or absorb) any arbitrary
amount of radiant energy.
 Planck said that atoms and molecules could emit (or absorb) energy only in discrete
quantities, like small packages or bundles. Planck gave the name quantum to the smallest
quantity of energy that can be emitted (or absorbed) in the form of electromagnetic
radiation.
Planck’s Quantum Theory
 The energy E of a single quantum of energy is given by
Where h is called Planck’s constant and ν is the frequency of radiation. The value of
Planck’s constant is 6.63 X 10 -34 J. s. Because ν = c/λ , this equation can also be expressed
as
According to quantum theory, energy is always emitted in integral multiples of hν ; for

example, hν , 2 hν , 3 hν and so forth, but never, for example, 1.67 hν or 4.98 hν. Therefore,
this equation can be again written as E= nhν, n is called quantum number.
Quantum effect depends on the mass of the object. The smaller the mass, the more likely
you will see quantum effects. Atoms, particularly electrons have small enough masses to
exhibit quantization of energy.
Photoelectric Effect
 In 1905, Albert Einstein used the quantum theory to solve another mystery in physics, the
photoelectric effect, a phenomenon in which electrons are ejected from the surface of
certain metals exposed to light of at least a certain minimum frequency, called the threshold
frequency (characteristics of the particular metal).
 The photoelectric effect could not be explained by the wave theory of light. Einstein
suggested that a beam of light is really a stream of particles. These particles of light are now
called photons. Using Planck’s quantum theory of radiation as a starting point, Einstein
deduced that each photon must possess energy E , given by the equation
 Calculate the energy (in joules) of (a) a photon with a wavelength of 5.00 X 104 nm (infrared
region) and (b) a photon with a wavelength of 5.00 X 10-2 nm (X ray region).
An apparatus for studying the photoelectric effect. Light of a certain
frequency falls on a clean metal surface. Ejected electrons are
attracted toward the positive electrode. The flow of electrons is
registered by a detecting meter. Light meters used in cameras are
based on photoelectric effect.
It needs a photon (h ) to eject an electron with energy ½ mv2.

• Removing electron from the metal requires light of a sufficiently high frequency (i.e. sufficiently high
energy) to break them free.
• Shining a beam of light onto a metal surface can be thought of as shooting a beam of particles—
photons—at the metal atoms.
• If the frequency of photons is such that hν is exactly equal to the energy that binds the electrons in the
metal, then the light will have just enough energy to knock the electrons loose. If we use light of a higher
frequency, then not only will the electrons be knocked loose, but they will also acquire some kinetic
energy. This situation is summarized by the equation
where KE is the kinetic energy of the ejected electron and W is the work function, which is a measure
of how strongly the electrons are held in the metal.
Rewrite the equation as
KE = hn – W, it shows that the more energetic the photon (that is, the higher the frequency),
the greater the kinetic energy of the ejected electron
The formula displays the wave-particle

dual nature of light. E is the energy of a light
particle or photon and n is the frequency of the
associated wave.
Therefore, neither the wave nor the particle view alone is a complete
description of light.
Problem: The work function of cesium metal is 3.42 X 10-19 J. (a) Calculate the minimum
frequency of light required to release electrons from the metal. (b) Calculate the kinetic
energy of the ejected electron if light of frequency 1.00 X 1015 s-1 is used for irradiating
the metal
Strategy: (a) The relationship between the work function of an element and the
frequency of light is given by Equation
The minimum frequency of light needed to dislodge an electron is the point where the
kinetic energy of the ejected electron is zero. (b) Knowing both the work function and
the frequency of light, we can solve for the kinetic energy of the ejected electron.
Confusing Features of Photoelectric Effect
Despite the idea of quantization, physicists still pictured energy as traveling in waves. But, the wave
model could not explain the second confusing observation, the flow of current when light strikes a metal.
Observation: the photoelectric effect. When monochromatic light of sufficient frequency shines on a
metal plate, a current flows. It was thought that the current arises because light transfers energy that
frees electrons from the metal surface. However, the effect had two confusing features, the presence of a
threshold frequency and the absence of a time lag:
• Presence of a threshold frequency. For current to flow, the light shining on the metal must have a
minimum, or threshold, frequency, and different metals have different minimum frequencies. But, the
wave theory associates the energy of light with its amplitude (intensity), not its frequency (color). Thus,
the theory predicts that an electron would break free when it absorbed enough energy from light of any
color.
• Absence of a time lag. Current flows the moment light of the minimum frequency shines on the metal,
regardless of the light’s intensity. But the wave theory predicts that with dim light there would be a time
lag before the current flows, because the electrons would have to absorb enough energy to break free.
Explanation of the observations of Photoelectric Effect
Compton Effect (Proof of particle nature of light)
 In 1923 A.H. Compton provided one more proof to the quantum theory or the photon theory.
 He was awarded Nobel Prize in 1927 for his discovery of what is now called the Compton Effect.
He demonstrated that : When X-rays of wavelength λ' struck a sample of graphite, an electron
was ejected and the X-rays scattered at an angle θ had longer wavelength λ (i.e. energy
decreased).
Explanation of Compton Effect
 Light radiation (X-rays) consisted of particles (photons), as a

continuous wave could not have knocked out the electron.
 He visualized that a photon of incident light struck a stationary
electron in graphite and hence lost some energy which
resulted in the increase of wavelength.
 This process could not have occurred unless light radiation
consisted of particles or photons.
Compton Effect
By assuming photon-electron collisions to be perfectly elastic, Compton found that the
shift in wavelength, d λ was given by the expression
where h is Planck’s constant, m the mass of an electron, c the velocity of light and θ the
angle of scattering.
• The expression shows that dλ is independent of the nature of the substance and
wavelength of the incident radiation.
• Given the wavelength of a photon, one can calculate the momentum of the electron
ejected.
Atomic Line
Element lineSpectra
spectrum
When light from electrically excited gaseous

atoms passes through a slit and is refracted by a
prism, it does not create a continuous spectrum,
or rainbow, as sunlight does. Instead, it creates a
line spectrum, a series of fine lines at specific
frequencies separated by black spaces.
Figure A shows the apparatus and the line spectrum of atomic hydrogen. Figure B shows that each spectrum is
characteristic of the element producing it.
Atomic Line Spectra
Atomic Line Spectra
Atomic Line Spectra
Pictorial
Graphical
Johann Balmer, School teacher

Just figured out that the lines fit a simple equation
Atomic Line Spectra
Flame test or fireworks
When white light passes

through hydrogen vapour,
absorption spectrum shows
dark lines
Atomic Line Spectrac
Atomic Line Spectra of H Atom
Atomic Line Spectra
Using data, not theory, the Swedish physicist Johannes Rydberg developed a
relationship, called the Rydberg equation, that predicted the position and wavelength
of any line in a given series:
Emission Spectrum of Hydrogen
IR
Visible
Ultraviolet
Figure: The energy levels in the hydrogen atom and
the various emission series. Each energy level
corresponds to the energy associated with an
allowed energy state for an orbit, as postulated by
Bohr
We Have Learned
Bohr’s Atomic Model
• Rutherford’s nuclear model of atom could not explain the position of electrons.
• Niels Bohr, in 1913, utilized the concepts of Planck and Einstein and applied a new
theory to the simplest atom hydrogen.
• Bohr set down some postulates to account for the stability of the hydrogen atom
and the line spectrum of the atom.
Bohr’s Atomic Model (Postulate - 1)
Energy level postulate:
 Electron is allowed to occupy only certain orbits of specific energies (energy levels).
 An electron in any of the allowed orbits will not spiral into the nucleus and therefore will not
radiate energy.
 Bohr attributed the emission of radiation by an energized hydrogen atom to the electron
dropping from a higher-energy allowed orbit to a lower one and emitting a quantum of energy
(a photon) in the form of light. Bohr showed that the energies that an electron in hydrogen
atom can occupy are:
RH = Rydberg constant for the hydrogen atom (2.18 X 10-18 J)

n = an integer called the principal quantum number (n = 1, 2, 3, . . . .)
Bohr’s Atomic Model (Postulate - 2)
Transition between Energy levels:
 An electron in an atom can change energy only by going from one energy level to another
energy level. By doing so, the electron undergoes a transition.
 According to Bohr, the emission of light from an atom occurs by transition of an electron from
higher energy level (initial energy level, Ei) to a lower energy level (final energy level, Ef).
Because this transition results in the

emission of a photon of frequency ν
and energy hν, we can write,
Defects of Bohr’s Atomic Model
 Bohr’s approach did not account for the emission spectra of atoms containing more than one
electron, such as atoms of helium and lithium
 In reality, Bohr’s theory accounted for the observed emission spectra of He+ and Li2+ ions, as
well as that of hydrogen. However, all three systems have one feature in common—each
contains a single electron. Thus, the Bohr model worked successfully only for the hydrogen
atom and for “hydrogenlike ions”.
 It cannot explain why extra lines appear in the hydrogen emission spectrum when a magnetic
field is applied
1) The Bohr Model provides an incorrect value for the ground state orbital angular momentum.
2) Duel nature of electron and the Heisenberg Uncertainty Principle because it considers electrons
to have both a known radius and orbit.
3) No explanation of fine structure (produced by electron spin-orbit coupling)-Existence of
additional quantum numbers.
4) It makes poor predictions regarding the spectra of larger atoms.
5) The Bohr Model does not explain fine structure and hyperfine structure (the interaction
between the magnetic field and nuclear spin) in spectral lines.
6) No explanation for Zeeman Effect and Stark Effect.
The Zeeman Effect: It was found that, when hydrogen

gas was excited in a magnetic field, the produced
emission spectrum was split. Bohr's model could not
account for this. Solved by accounting for the existence of a
tiny magnetic moment of each electron.
The Stark effect is the shifting and splitting of spectral lines

of atoms and molecules due to the presence of an external
electric field. It is the electric-field analogue of the Zeeman
effect, where a spectral line is split into several components due
to the presence of the magnetic field.
Bohr-Sommerfield Atomic Model
Atomic radius
Atomic radius
Energy of an electron in Atomic orbit
The potential energy of the electron in the field of the positive proton
point charge is U(r) = -qeV(r) = - keqe2/r. The total energy is the sum of
the electron's kinetic energy and its potential energy.
Energy of an electron in Atomic orbit
When that electron comes close to the nucleus, the stability

increases due to the loss of energy of electron and thus the
energy of electron becomes less negative. That's why the electrons
energy is taken as negative.
PROBLEM: A hydrogen atom absorbs a photon of UV light and its electron enters the n = 4 energy
level. Calculate (a) the change in energy of the atom and
(b) the wavelength (in nm) of the photon.
PLAN: (a) The H atom absorbs energy, so Efinal > Einitial. We are given nfinal = 4, and Figure 7.11
shows that ninitial = 1 because a UV photon is absorbed. We apply the previous equation to
find ΔE.
(b) Once we know ∆E, we find frequency and wavelength.
Calculate the wavelength (in nm) of a photon emitted by a hydrogen
atom when its electron drops from the n = 5 state to the n = 3 state.
1
E photon = ΔE = RH ( 12 )
n n2
i f
= 2.18 x 10-18 J x (1/25 - 1/9)
= -1.55 x 10-19 J
E photon = h x c / λ
λ = h x c / Ephoton
= 6.63x10-34(J•s) x3.00x108 (m/s)/1.55 x10-19J
= 1280 nm
Wave–particle duality
Dual Nature of Electron
Why energy of H electron is quantized? Or
Why electron in a Bohr atom is restricted to orbiting the nucleus at certain fixed distances?
In 1924, French Physicist Louis de Broglie reasoned that if light waves can behave like a stream
of particles (photons), then perhaps particles such as electrons can possess wave properties.
De Broglie’s reasoning led to the conclusion that waves can behave like particles and particles
can exhibit wavelike properties.
According to de Broglie, an electron bound to the nucleus behaves like a standing wave
• If an electron behave like a standing wave, the length of the wave must fit the circumference of
the orbit exactly. Otherwise, the wave would partially cancel itself on each successive orbit.
Eventually the amplitude of the wave would be reduced to zero, and the wave would not exist.
• The relation between the circumference of an allowed orbit and the wavelength of the electron
is given by,
2πr = nλ r= radius of orbit
λ= wavelength of the electron wave
n= 1, 2, 3……integer
As n is an integer, r can have a certain value as n increases from 1 to higher. Energy of the electron
depends on the size of orbit (r), its value must be quantized.
Relation Between de Broglie Equation and Bohr’s
Hypothesis of Atom
In 1924, Louis de Broglie reasoned that if light
waves can behave like a stream of particles
(a) The circumference of the (b)The circumference of

orbit is equal to an integral the orbit is not equal to an
number of wavelengths. This is integral number of
an allowed orbit. wavelengths. As a result,
the electron wave does not
close in on itself. This is a
non allowed orbit.
An electron moving in a closed orbit is considered as a standing wave. Planck’s equation can be
applied to this electron wave. So,
E = hν
From Einstein equation, we have:
E = mc2
Therefore, mc2 = hν
or, mc = hν/c = h/λ
Hence, λ = h/mc
Applying the above equation on electron moving with velocity v and associated with
wavelength λ, the de Broglie relationship is obtained as:
λ = h/mv,
Shortly after de Broglie introduced his equation, in 1927 Clinton Davisson and Lester Germer in the
United States and G. P. Thomson in England demonstrated that electrons do indeed possess wavelike
properties.
 By directing a beam of electrons through a thin piece of gold foil, Thomson obtained a set of
concentric rings on a screen, similar to the pattern observed when X rays (which are waves) were
used.
Figure: (a) X-ray diffraction pattern of
aluminum foil. (b) Electron diffraction
of aluminum foil. The similarity of
these two patterns shows that
electrons can behave like X rays and
display wave properties.
The wavelength of waves associated with a moving material particle (matter waves) is called de Broglie’s
wavelength. The de Broglie’s equation is true for all particles, but it is only with very small particles, such as
electrons, that the wave-like aspect is of any significance. Large particles in motion though possess wavelength,
but it is not measurable or observable. Let us, for instance consider de Broglie’s wavelengths associated with
two bodies and compare their values.
Major observations and theories
leading from particulate,
massive, wavelike classical
theory to quantum theory
Davison and Germers Experiment
 de Broglie’s revolutionary suggestion that moving electrons had waves of definite

wavelength associated with them, was put to the acid test by Davison and Germer (1927).
 They demonstrated the physical reality of the wave nature of electrons by showing that a
beam of electrons could also be diffracted by crystals just like light or X-rays.
 They observed that the diffraction patterns thus obtained were just similar to those in case of
X-rays.
 Thomson ruled out this possibility, showing that the electron beam as it emerged from the
crystals, underwent deflection in the electric field towards the positively charged plate.
 Davison and Germer studied the scattering of slow moving electrons by reflection from the
surface of nickel crystal
Experimental procedure
 They obtained electrons from a heated filament and passed the stream of electrons through charged plates kept at a
potential difference of V esu.
 Due to the electric field of strength V × e acting on the electron of charge e, the electrons emerge out with a uniform
velocity v units. The kinetic energy mv acquired by an electron due to the electric field shall be equal to the electrical
force. Thus,
 If a potential difference of 150 volts be applied, the wavelength of electrons emerging out is λ = 1 Å. Similarly if a
potential difference of 1500 volts be created, the electrons coming out shall have a wavelength 0.1 Å.
 It is clear, therefore, that electrons of different wavelengths can be obtained by changing the potential drop. These
wavelengths are comparable with those of X-rays and can undergo diffraction.
 Since diffraction is a property exclusively of wave motion, Davison and Germer’s ‘electron diffraction’ experiment
established beyond doubt the wave nature of electrons.
Heisenberg Uncertainty Principle
After exploring the wave property of electron, another question arise: How can the “position” of
a wave be specified? We cannot define the precise location of a wave because a wave extends in
space.
To describe the problem of trying to locate a subatomic particle that behaves like a wave, Werner
Heisenberg stated that “it is impossible to know simultaneously both the momentum p (defined
as mass times velocity) and the position of a particle with certainty”. Mathematically,
∆x and ∆p are the uncertainties in measuring the position and momentum of the particle,
respectively.
Heisenberg Uncertainty Principle
Applying the Heisenberg uncertainty principle to the hydrogen atom, we see that in reality the electron does
not orbit the nucleus in a well-defined path, as Bohr thought.
If it did, we could determine precisely both the position of the electron (from its location on a particular orbit)
and its momentum (from its kinetic energy) at the same time: a violation of the uncertainty principle.
Bohr’s suggestion that the energy of an electron in an atom is quantized remains unchallenged. But his
theory did not provide a complete description of electronic behavior in atoms.
In 1926 the Austrian physicist Erwin Schrödinger, using a complicated mathematical technique, formulated
an equation that describes the behavior and energies of submicroscopic particles in general.
Schrödinger Equation (1926)
m = mass of the electron

E = Total energy of the electron
V = Potential energy of the electron
ψ = Wave function
The probability of finding the electron over

all the space from plus infinity to minus
infinity must be equal to one.
The probability of finding an electron at a
point x, y, z is ψ2, so
 This equation incorporates both particle behavior, in terms of mass m , and wave behavior, in
terms of a wave function ψ (psi), which depends on the location in space of the system (such
as an electron in an atom).
 The wave function is obtained by solving Schrödinger equation,
 The wave function itself has no direct physical meaning. Its square, ψ2 , gives the probability of
finding the particle within a region of space.
 We can obtain the probability of finding an electron at a certain point in a hydrogen atom.
Although we cannot say that electron will definitely at a particular position at a given time, we
can say that the electron is likely to be at this position.
Schrödinger Equation
Left figure is a representation of the electron density distribution surrounding the nucleus in
the hydrogen atom. It shows a high probability of finding the electron closer to the nucleus.
Right figure shows the probability of finding the electron within shells at various distances
from the nucleus, which means that the radial probability is greatest at some distance from the
nucleus. This distance just happens to equal the radius that Bohr calculated for an electron
orbit in his model.
Quantum Mechanical Description of H Atom
 The Schrödinger equation specifies the possible energy states of the electron in a hydrogen
atom and identifies the corresponding wave functions (ψ) .
 These energy states and wave functions are characterized by a set of quantum numbers, with
which we can construct a comprehensive model of the hydrogen atom.
 The square of the wave function, ψ2, defines the distribution of

electron density in three-dimensional space around the nucleus.
 Regions of high electron density represent a high probability of
locating the electron, whereas the opposite holds for regions of
low electron density.
H atom
To distinguish the quantum mechanical description of an atom from Bohr’s model, we speak
of an atomic orbital, rather than an orbit.
An atomic orbital can be thought of as the wave function of an electron in an atom. An

atomic orbital is pictured quantitatively by describing the region of space where there is high
probability of finding the electrons. Atomic orbital has a definite shape.
An atomic orbital, therefore, has a characteristic energy, as well as a characteristic

distribution of electron density.
In Schrödinger’s Wave Equation, the symbol ᴪ represents the amplitude of the spherical wave.
For hydrogen atom, Schrödinger’s Wave Equation gives the wave function of the electron (with energy = –
2.18 × 10–11 ergs) situated at a distance ‘r’,
ψ = C1e – C2r
where C1 and C2 are constants. The square of the amplitude ψ2 is proportional to the density of the wave.
Max Born interpreted the wave equations on the basis of probabilities. Even if an electron be considered
as a particle in motion around the nucleus, the wave equation may be interpreted in terms of probability
or relative chance of finding the electron at any given distance from the nucleus.
The space characteristic of an electron is best described in terms of distribution function given by
D = 4πr2 ψ2
The numerical value of ‘D’ denotes the probability or chance of finding the electron in a shell of radius r
and thickness dr, or of volume 4πr2 dr. Substituting for ψ we have,
D = 4πr2 (C1e – C2r)2 When r = 0 or ∝ , the probability
function D becomes equal to zero.
 However, it is possible to choose a value of r such that there is 90-95% chance of finding the electron at this
distance.
 For the hydrogen atom, this distance is equal to 0.53 × 10-8 cm or 0.53 Å.
 If the probability distribution be plotted against the distance r from the nucleus, the curve obtained is shown in the
figure.
 The probability distribution is maximum at the distance 0.53 Å and spherically symmetrical. This distance
corresponds to Bohr’s first radius a0.
 When the electron gets excited and it is raised from n to higher energy levels (say n = 2 or n = 3), the solution of
wave equation gives sets of value of ψ2 which give different shapes to the space distribution of the electron.
Evolution of atomic model
 For a given type of atom, there are a number of solutions to the wave equation
which are acceptable
 Each orbital may be described uniquely by a set of three quantum numbers, n, I and
m. (These are the same quantum numbers - principal, subsidiary and magnetic - as
were used in the Bohr theory). i.e.
Ψ (Psi) is a function of three quantum numbers → n, l, m.

Quantum Numbers
Four quantum numbers:
1. Principal quantum number (n)
2. Angular momentum quantum number (l)
3. Magnetic quantum number (ml)
4. Spin quantum number (ms)
Quantum numbers 1-3 are required to describe the distribution of electrons (atomic orbital)
in hydrogen and other atoms. These numbers are derived from the mathematical solution of
the Schrödinger equation for the hydrogen atom. Spin quantum number describes the
behavior of a specific electron and completes the description of electrons in atoms.
Principle Quantum Number (n)
The principal quantum number also relates to the average distance of the electron from
the nucleus in a particular orbital. The larger the n, the greater the average distance of an
electron in the orbital from the nucleus and therefore the larger the orbital.
n=2 n=3
n=1
Angular Momentum Quantum Number (l)
It describes the shape of the orbital occupied by the electron. It’s values depend on the
value of the principal quantum number, n . l = 0 to n-1
If n=1, there is only one possible value of l; that is, l= n-1 = 0.
If n=2 or 3, what is the value of l?
A collection of orbitals with the same value of n is frequently called a shell. One or more
orbitals with the same n and different l values are referred to as subshells of a given shell.
For example, the shell with n= 2 is composed of two subshells, l= 0 and 1. These subshells
are called the 2s and 2p subshells where 2 denotes the value of n , and s and p denote
the values of l.
Angular momentum quantum number (l)
The value of l is generally designated by the letters s , p , d, . . . as follows:
When l=0, the orbital is spherical and is called an s orbital

When l=1, the orbital is dumb-bell shaped and is called a p orbital
When l=2, the orbital is double dumb-bell shaped and is called a d orbital
When l=3, a more complicated f orbital is formed
The letters s, p, d, f come from the spectroscopic terms sharp, principal, diffuse and
fundamental, which were used to describe the lines in the atomic spectra.
Magnetic quantum number (ml)
It describes the orientation of the orbital in space. Within a subshell, the value of ml
depends on the value of l. For a certain value of l, there are (2l + 1) integral values of ml as
follows:
What is the values of ml if l = 0 or 1 or 2?

Consider a situation in which n=2 and l=1. The values of n and l indicate what?
It indicates a 2p subshell, and in this subshell we have three 2p orbitals (because there are
three values of ml, given by -1, 0 and 1). The orbitals have the same shape but different
orientation in space
Magnetic quantum number (ml)
Info from Schrodinger Equation
Shell – electrons with the same value of n

Subshell – electrons with the same values of n and l
Orbital – electrons with the same values of n, l, and ml

Orbital Groups
Examination of a list of all the allowed solutions to the wave equation shows that the
orbitals fall into groups.
In the first group of solutions the value of the wave function ψ, and hence the probability of
finding the electron ψ2, depends only on the distance r from the nucleus, and is the same in
all directions.
Ψ = f(r)
This leads to a spherical orbital and occurs when l=0. These are called s orbital. When l=0, m
is also 0. So there is only one such orbital for each value of n.
Orbital Groups
In the second group of solutions to the wave equation, ψ depends both on the distance r from
the nucleus, and on the direction in space (x, y or z). Orbital of this kind occurs when l=1. These
are called p orbitals and there are three possible values of the magnetic quantum number (m = -
1, 0, +1). Therefore, there are three orbitals which are identical in energy, shape and size, which
differ only in their direction in space. These three solutions to the wave equation may be
written,
Ψx = f(r) . f(x)
Ψy = f(r) . f(y)
Ψz = f(r) . f(z)
As these are identical in energy, three degenerate p orbitals occur for each of the values of n =
2, 3, 4……
Orbital Groups
In the third group of solutions to the wave equation depends on the distance r from the
nucleus, and also on two directions in space, for example,
Ψ = f(r) . f(x) . f(y)
These group of orbitals has l=2. These are called d orbitals. There are five solutions
corresponding to m= -2, -1, 0, +1 and +2. These are all equal in energy. Therefore, five
degenerate d orbitals occur for each of the values of n = 3, 4, 5……
A further set of solution s occurs when l=3, and these are called f orbitals. There are seven
values of m= -3, -2, -1, 0, +1. +2 and +3. Seven degenerate d orbitals are formed when of n = 4,
5, 6……
Spin Quantum Number (ms)
It refers to the two possible orientation of the spin axis of an electron. The values are +1/2 and -
1/2.
An electron acts as though it were spinning on its axis like the earth. Such an electron spin would
give rise to a circulating electric charge that would generate a magnetic field. In this way, an
electron behaves like a small bar magnet, with a north and south pole.
Spin Quantum Number (ms)
The Spin Quantum Number begins with an experiment by Otto Stern and Walther
Gerlach, which demonstrated that a beam of atoms split evenly into two. This is
due to a property of the electrons that causes them to generate their own
magnetic field and, consequently, their own internal momentum.
Applying the rules for quantum number
1) State whether each of the following sets of quantum numbers is permissible for an electron in
an atom.
a. n = 1, l = 1, ml = 0, ms = +1/2
b. n = 3, l = 1, ml = -2, ms = -1/2
c. n = 2, l = 1, ml = 0, ms = +1/2
d. n = 2, l = 0, ml = 0, ms = 1
2) Supply the missing quantum numbers and sublevel names.

For Multi-electron System
The Schrödinger equation works nicely for the simple hydrogen atom and related ions such as
He+ and Li2+, but only approximate solution could be obtained for multi-electron system.
Fortunately, chemists and physicists have learned to get around this kind of difficulty by
approximation.
For example, although the behavior of electrons in multi-electron atoms is not the same as in
the hydrogen atom, we assume that the difference is probably not too great.
Thus, we can use the energies and wave functions obtained from the hydrogen atom as good
approximations of the behavior of electrons in more complex atoms.
Radial and Angular Part of Wave Function
For most calculations, it is simpler to solve the wave equation if the cartesian coordinates x,
y and z are converted into polar coordinates r, θ and φ.
The coordinates of the point A measured from the origin are x, y

and z in cartesian coordinates, and r, θ and φ in polar
coordinates. The two sets of coordinates are related by the
following expressions:
z = r cosθ Figure: The relationship between
cartesian and polar coordinates
y = r sin θ sin φ
x = r sin θ cos φ
Radial and Angular Part of Wave Function
The Schrödinger equation is usually written as:
where,
Changing to polar coordinates, becomes
The solution of this form is,

Radial and Angular Function
R(r) is a function that depends on the distance from the nucleus, which in turn depends on
the quantum numbers n and l.
Θ(θ) is an function of θ (theta), which depends on the quantum numbers l and m
Ф(φ) is a function of φ (Phi), which depends only on the quantum number m
This equation may be written as, ψ = R(r)nl. Aml

Radial and Angular Function
ψ = R(r)nl. Aml
This splits the wave function into two parts which can be solved separately:
1. R(r) the radial function, which depends on the quantum numbers n and l.
2. Aml, the total angular wave function, which depends on the quantum numbers l and m
The radial function has no physical meaning, but R2 gives the probability of finding the
electron in a small volume near the point at which R is measured.
Electron Probability Density vs. Radial Probability
Probability Density
(a) Density dot shows electron probability. (b)

[Probability density plot] The electron probability
density is greatest at r=0, i.e. at the nucleus and
falls off with increasing r. The line never actually
reaches the horizontal axis, therefore, the
probability of finding the electron at very large
Figure: Probability of finding the electron in the values of r is very small but not zero
ground state of the hydrogen atom at different
points in space
Radial Probability
Radial Probability is the probability of finding an electron at a distance r from the nucleus. It can be
calculated by adding together the probabilities of an electron being at all points on a series of x
spherical shells of radius r1, r2, r3,……, rx-1, rx.
we are dividing the atom into very thin concentric

shells, much like the layers of an onion, and
calculating the probability of finding an electron on
each spherical shell. Recall that the electron
probability density is greatest at r = 0, so the density
of dots is greatest for the smallest spherical shells.
(b) A plot of Ψ2 versus r shows that the electron probability density is
greatest at r = 0 and falls off smoothly with increasing r. The density of
the dots is therefore greatest in the innermost shells (c) The surface
area of each shell, given by 4πr2, increases rapidly with increasing r. (d)
If we count the number of dots in each spherical shell, we obtain the
total probability of finding the electron at a given value of r. Because the
surface area of each shell increases more rapidly with increasing r than
the electron probability density decreases, a plot of electron probability
versus r (the radial probability) shows a peak at a particular distance.
When r is very small, the surface area of a spherical shell is so small that
the total probability of finding an electron close to the nucleus is very
low; at the nucleus, the electron probability vanishes because the
surface area of the shell is zero.
 For the hydrogen atom, the peak in the radial probability plot occurs at r = 0.529 Å
(52.9 pm), which is exactly the radius calculated by Bohr for the n = 1 orbit.
 Thus the most probable radius obtained from quantum mechanics is identical to
the radius calculated by classical mechanics.
 In Bohr’s model, however, the electron was assumed to be at this distance 100% of
the time, whereas in the Schrödinger model, it is at this distance only some of the
time.
 The difference between the two models is attributable to the wavelike behavior of
the electron and the Heisenberg Uncertainty Principle.
Probability Densities for the 1s, 2s, and 3s Orbitals of the Hydrogen Atom (a) The electron probability
density in any plane that contains the nucleus is shown. Note the presence of circular regions, or nodes, where
the probability density is zero. (c) In these plots of electron probability as a function of distance from the
nucleus (r) in all directions (radial probability), the most probable radius increases as n increases, but the
2s and 3s orbitals have regions of significant electron probability at small values of r.
• Note that all three orbitals (1s, 2s, 3s) are spherically symmetrical.
• For the 2s and 3s orbitals, however (and for all other s orbitals as well), the electron
probability density does not fall off smoothly with increasing r.
• Instead, a series of minima and maxima are observed in the radial probability plots
(part (c) in the figure). The minima correspond to spherical nodes (regions of zero
electron probability), which alternate with spherical regions of nonzero electron
probability.
Radial Distribution Functions
For a given value of r the number of
surface area is 4πr2(2D), so the
probability of the electron being at a
distance r from the nucleus is 4πr2 R2.
This is called the radial distribution
function (3D).
Figure: Radial distribution function

for various orbitals in the H atom.
• Radial probability is always small near the nucleus and zero at the nucleus
• The position of principal maximum depends on n and l values
• The most probable distance increases markedly as the principal quantum number increases. In
other way, for a fixed l, as n increases, the position of principal maximum moves to larger r values
• For a fixed n value, the most probable radius decreases slightly as the subsidiary quantum
number increases
• No. of radial nodes = n-l-1
Shape of atomic orbitals
The 1s, 2s, and 3s orbitals.
The 3d
orbitals
The 3d orbitals
The 4fxyz orbital, one of the seven 4f orbitals.
s Orbitals
Three things happen to s orbitals as n increases:
1. They become larger, extending farther from the nucleus.
2. They contain more nodes. This is similar to a standing wave that has regions of significant amplitude
separated by nodes, points with zero amplitude.
3. For a given atom, the s orbitals also become higher in energy as n increases because of their increased
distance from the nucleus.
Orbitals are generally drawn as three-dimensional surfaces that enclose 90% of the electron density, as was
shown for the hydrogen 1s, 2s, and 3s orbitals. Although such drawings show the relative sizes of the orbitals,
they do not normally show the spherical nodes in the 2s and 3s orbitals because the spherical nodes lie inside
the 90% surface. Fortunately, the positions of the spherical nodes are not important for chemical bonding.
This makes sense because bonding is an interaction of electrons from two atoms which will be most sensitive
to forces at the edges of the orbitals.
p Orbitals
a b
Figure: Electron Probability Distribution for a Hydrogen 2p Orbital The nodal plane of zero electron density
separates the two lobes of the 2p orbital. (a) Because this orbital has two lobes of electron density arranged along
the z axis, with an electron density of zero in the xy plane (i.e., the xy plane is a nodal plane), it is a 2pz orbital. (b) In
each case, the phase of the wave function for each of the 2p orbitals is positive for the lobe that points along the
positive axis and negative for the lobe that points along the negative axis. It is important to emphasize that these
signs correspond to the phase of the wave that describes the electron motion, not to positive or negative charges.
p Orbitals
Just as with the s orbitals, the size and complexity of the p orbitals for any atom
increase as the principal quantum number n increases. The shapes of the 90%
probability surfaces of the 3p, 4p, and higher-energy p orbitals are, however,
essentially the same.
d Orbitals
The surfaces shown enclose 90% of the total electron probability for the five hydrogen 3d orbitals
d Orbitals
The hydrogen 3d orbitals have more complex shapes than the 2p orbitals. All five 3d orbitals contain
two nodal surfaces, as compared to one for each p orbital and zero for each s orbital. In three of
the d orbitals, the lobes of electron density are oriented between the x and y, x and z,
and y and z planes; these orbitals are referred to as the 3dxy, 3dxz, and 3dyz orbitals, respectively. A
fourth d orbitals has lobes lying along the x and y axes; this is the 3dx -y orbital. The fifth 3d orbital,
2 2
called 3dz orbital, has a unique shape. It looks like a 2p orbital combined with an additional doughnut of
2
electron probability lying in the xy plane. Despite its peculiar shape, it is mathematically equivalent to
the other four and has the same energy.
Like the s and p orbitals, as n increases, the size of the d orbitals increases, but the overall shapes
remain similar
Atomic Orbitals
Orbital Energies
Figure: Orbital Energy Level Diagram for the Hydrogen
Atom (considering atoms or ions with only a single
electron). Each box corresponds to one orbital. Note
that the difference in energy between orbitals
decreases rapidly with increasing values of n. The
orbital energies depend on only the principal
quantum number n. Consequently, the energies of the
2s and 2p orbitals of hydrogen are the same; the
energies of the 3s, 3p, and 3d orbitals are the same;
and so forth.
Orbital Energies
 Level Diagram for the Hydrogen Atom (considering atoms or ions with only a single electron).
 Each box corresponds to one orbital. Note that the difference in energy between orbitals decreases
rapidly with increasing values of n. The orbital energies depend on only the principal quantum
number n.
 Consequently, the energies of the 2s and 2p orbitals of hydrogen are the same; the energies of the 3s,
3p, and 3d orbitals are the same; and so forth.
 The energies of the orbitals in any species with only one electron can be calculated by a minor
variation of Bohr’s equation, which can be extended to other single-electron species by incorporating
the nuclear charge Z (the number of protons in the nucleus):
E = -RH(z2/n2)
Orbital Energies
 In general, both energy and radius decrease as the nuclear charge increases. As a result of the Z2
dependence of energy in energy Equation, electrons in the 1s orbital of carbon, which has a nuclear
charge of +6, lie roughly 36 times lower in energy than those in the hydrogen 1s orbital, and the 1s orbital
of tin, with an atomic number of 50 is roughly 2500 times lower still.
 The most stable and tightly bound electrons are in orbitals (those with the lowest energy) closest to the
nucleus.
For example, in the ground state of the hydrogen atom, the single electron is in the 1s orbital, whereas in the
first excited state, the atom has absorbed energy and the electron has been promoted to one of the n = 2
orbitals. In ions with only a single electron, the energy of a given orbital depends on only n, and all subshells
within a principal shell, such as the s, px, py, and pz orbitals, are degenerate.
Effective Nuclear Charge
• For an atom or an ion with only a single electron, we can calculate the potential energy by
considering only the electrostatic attraction between the positively charged nucleus and the
negatively charged electron.
• When more than one electron is present, however, the total energy of the atom or the ion
depends not only on attractive electron-nucleus interactions but also on repulsive electron-
electron interactions.
• When there are two electrons, the repulsive interactions depend on the positions
of both electrons at a given instant, but because we cannot specify the exact positions of the
electrons, it is impossible to exactly calculate the repulsive interactions.
• Consequently, we must use approximate methods to deal with the effect of electron-electron
repulsions on orbital energies.
• If an electron is far from the nucleus, then at any given moment, most of the other electrons will
be between that electron and the nucleus. Hence the electrons will cancel a portion of the positive charge
of the nucleus and thereby decrease the attractive interaction between it and the electron farther away.
• As a result, the electron farther away experiences an effective nuclear charge (Zeff) that is less than the
actual nuclear charge Z. This effect is called electron shielding.
• If an electron is very close to the nucleus, then at any given moment most of the other electrons are farther
from the nucleus and do not shield the nuclear charge. At r ≈ 0, the positive charge experienced by an
electron is approximately the full nuclear charge, or Zeff ≈ Z.
• At intermediate values of r, the effective nuclear charge is
somewhere between 1 and Z: 1 ≤ Zeff ≤ Z.
• Thus the actual Zeff experienced by an electron in a given orbital

depends not only on the spatial distribution of the electron in that
orbital but also on the distribution of all the other electrons
present.
Lists the values of Zeff for the electrons in

a potassium atom. Although, K (Z=19)
has a nuclear charge of 19+, all of its
electrons have Zeff <19.
Shielding and energy levels.

A, Within an energy level, each electron shields (red arrows) other electrons
from the full nuclear charge (black arrows), so they experience a lower Zeff.
B, Inner electrons shield outer electrons much more effectively than electrons in
the same energy level.
Effective Nuclear Charge and Orbital Energy
Within a given principal shell of a multielectron atom, the
orbital energies increase with increasing l. An ns orbital
always lies below the corresponding np orbital, which in
turn lies below the nd orbital. These energy differences are
caused by the effects of shielding and penetration, the
extent to which a given orbital lies inside other filled
orbitals.
For example, an electron in the 2s orbital penetrates inside a filled 1s orbital more than an electron in a 2p orbital does.
Hence in an atom with a filled 1s orbital, the Zeff experienced by a 2s electron is greater than the Zeff experienced by a
2p electron. Consequently, the 2s electron is more tightly bound to the nucleus and has a lower energy, consistent with
the order of energies.
Effective Nuclear Charge and Orbital Energy
Although a 2s electron spends most of its time (on average) slightly farther from the nucleus than a 2p
electron, the electron density near the nucleus is actually greater for the 2s electron (see the small maximum
for the 2s orbital in Figure). For this reason, the 2s orbital is said to be more “penetrating” than the 2p
orbital. Therefore, a 2s electron is less shielded by the 1s electrons and is more strongly held by the nucleus.
In fact, for the same principal quantum number n, the penetrating power decreases as the angular
momentum quantum number / increases, or
s>p>d>f>…
Because the stability of an electron is determined by the strength of its attraction to the nucleus, it follows
that a 2s electron will be lower in energy than a 2p electron.
To put it another way, less energy is required to remove a 2p electron than a 2s electron because a 2p
electron is not held quite as strongly by the nucleus. The hydrogen atom has only one electron and, therefore,
is without such a shielding effect.
Energy of the Orbitals
Figure: Orbital Energy Level Diagram for a Typical Multielectron Atom
Because of the effects of shielding and the different radial distributions of

orbitals with the same value of n but different values of l, the different
subshells are not degenerate in a multi-electron atom. For a given value
of n, the ns orbital is always lower in energy than the np orbitals, which
are lower in energy than the nd orbitals, and so forth. As a result, some
subshells with higher principal quantum numbers are actually lower in
energy than subshells with a lower value of n; for example, the 4s orbital
is lower in energy than the 3d orbitals for most atoms.
Filling of the Orbitals
Figure: The order in which atomic subshells are
filled in a many-electron atom. Start with the 1s
orbital and move downward, following the
direction of the arrows. Thus, the order goes as
follows: 1s , 2s , 2p , 3s , 3p , 4s , 3d , . . . .

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Chemistry: The Central Science

To answer these questions, atomic theory developed. The concept of an atom is

Thomson proposed that an atom could be thought of as

First, most of the alpha particles traveled right through the

 A typical atomic radius is about 100 pm, whereas the radius of

 Although the protons are confined to the nucleus of the atom,

 How are the electrons distributed in this space?

 What is the role of electrons in atomic stability, chemical bond formation?

 In stable atoms, the number of protons is equal to the number of electrons

 The type of atom is determined by the number of protons it has

 The number of protons in an atom is equal to the atomic number

 The sum of the number of protons and neutrons in a particular atom is

 Valence electrons are the outermost electrons

1) Dual character of the electromagnetic radiation which means that

A wave can be characterized by it’s wavelength, height and

Wavelength is usually expressed in units of meters, centimeters, or nanometers, and

3. Line spectra of atoms with the special reference to hydrogen

According to quantum theory, energy is always emitted in integral multiples of hν ; for

It needs a photon (h ) to eject an electron with energy ½ mv2.

The formula displays the wave-particle

Explanation of Compton Effect

 Light radiation (X-rays) consisted of particles (photons), as a

When light from electrically excited gaseous

Johann Balmer, School teacher

Flame test or fireworks

When white light passes

RH = Rydberg constant for the hydrogen atom (2.18 X 10-18 J)

Because this transition results in the

The Zeeman Effect: It was found that, when hydrogen

The Stark effect is the shifting and splitting of spectral lines

When that electron comes close to the nucleus, the stability

(a) The circumference of the (b)The circumference of

 de Broglie’s revolutionary suggestion that moving electrons had waves of definite

m = mass of the electron

The probability of finding the electron over

 The square of the wave function, ψ2, defines the distribution of

An atomic orbital can be thought of as the wave function of an electron in an atom. An

An atomic orbital, therefore, has a characteristic energy, as well as a characteristic

Ψ (Psi) is a function of three quantum numbers → n, l, m.

When l=0, the orbital is spherical and is called an s orbital

What is the values of ml if l = 0 or 1 or 2?

Shell – electrons with the same value of n

Orbital – electrons with the same values of n, l, and ml

2) Supply the missing quantum numbers and sublevel names.

The coordinates of the point A measured from the origin are x, y

Changing to polar coordinates, becomes

The solution of this form is,

Θ(θ) is an function of θ (theta), which depends on the quantum numbers l and m

Ф(φ) is a function of φ (Phi), which depends only on the quantum number m

This equation may be written as, ψ = R(r)nl. Aml

(a) Density dot shows electron probability. (b)

we are dividing the atom into very thin concentric

Figure: Radial distribution function

• At intermediate values of r, the effective nuclear charge is

somewhere between 1 and Z: 1 ≤ Zeff ≤ Z.

• Thus the actual Zeff experienced by an electron in a given orbital

Lists the values of Zeff for the electrons in

Shielding and energy levels.

Because of the effects of shielding and the different radial distributions of

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