Atomic Structure

Instructor: Prof. Cecil K. Kingondu

Office: Room # 19 (Porta Cabins Behind Engineering Building

Email: Kingonduc@biust.ac.bw

Tel: 493 1880

 Learning Outcomes – Atomic Structure

After studying this chapter, a student will be able to:

• Show the relationship between frequency, wavelength, & speed of electromagnetic radiation & to
calculate energy, frequency, or wavelength via Planck equation.
• Explain the contributions of Bohr model in determining the structure of the hydrogenic atom, its
limitations & refinement.
• Describe the electron distribution of an atom via Bohr model.
• Recognise the significance of the deBroglie equation, Heisenberg uncertainty principle, & the
Schrodinger wave equation in quantum theory.
• Describe electrons through quantum numbers (n, l, & ml ) & recognise interconversion between the
quantum numbers.
• Describe the periodic properties of atoms & ions.
Wave Nature of Electromagnetic Radiation

James Maxwell (1870) suggested that when electrically charged particle moves
under acceleration, alternating electrical and magnetic fields are generated and
transmitted.
➢ These fields are transmitted in the forms of waves called
electromagnetic waves or electromagnetic radiation.

➢ Light is one of these radiations with oscillating electric and

magnetic character

➢ Electromagnetic waves do not require medium and thus can

move in vacuum, not like sound waves which require a medium.
Electromagnetic Spectrum

➢ There are many types of electromagnetic radiations, which differ from

one another in wavelength (or frequency). These constitute what is
called electromagnetic spectrum.

➢ USES: Radio frequency region used for broadcasting; microwave region for radar;
infrared region for heating; ultraviolet region is a component of sun’s radiation.
The tiny portion, visible light, is only part which our eyes can see.
Electromagnetic Radiation: Visible Light, Relation Between Color and Wavelength

➢ Visible light constitutes a very small portion of the electromagnetic spectrum covering from on 400 to 700 nm.

➢ In the visible light region, many things including chemicals in the lab can be identified by their color e.g.
Nitrogen dioxide is brown and potassium permanganate is purple in color.
 Wave Nature of Light: Wavelength and Frequency
➢ These radiations are characterised by two properties, namely,
frequency (n ) and wavelength (l).

➢ The SI unit for frequency (n ) is hertz (Hz, s–1), after Heinrich Hertz.

➢ It is defined as the number of waves that pass a given point in one second.

➢ Wavelength has the units of length and as you know that the SI units of
length is meter ( 1 m = 10-9 nm).

➢In vacuum, all types of electromagnetic radiations, regardless of wavelength, travel

at the same speed, 2.997925 × 108 m s–1.
➢ This is called speed of light and is given the symbol ‘c‘.

➢The frequency (n), wavelength (l) and velocity of light (c) are related by:

c=nl

➢ The other commonly used quantity specially in spectroscopy, is the

wavenumber (n).

➢ It is defined as the number of wavelengths per unit length

➢Its units are reciprocal of wavelength unit (1/ l). (cm–1 is used for
wavenumber though not SI unit)
Example: Relationship between Wavelength and Frequency
You sit in your warm summer evening watching the red sky (l = 625 nm) at sunset and listening to
music from your balcony on a CD player. The CD player using a laser to read the music stored in the CD which has a
frequency 3.84 x 1014 s-1

a) What is the frequency of the radiation from the red sky?

b) What is the wavelength of the laser in nm?

Solution

Information given: Wavelength of the sky’s red color – 625 nm

Frequency of the laser - 3.84 x 1014 s-1
Information implied: Frequency of the sky’s radiation
Wavelength of the laser in nm

a) Wavelength in meters = 625 nm x (1 x 10-9 m/ 1 nm) = 6.25 x 10-9 m

Frequency  = c/ l = [2.998 x108 ms-1]/[625 x 10-9 m] = 4.80 x 1014 s-1

b) Wavelength l = c/ = [2.998 x108 ms-1]/[3.84 x 1014 s-1] = 7.81 x 10-7 m

Wavelength in nm = 7.81 x 10-7 m x [1 nm/1x 10-9 m] = 781 nm

Particle Nature of Light: Quantized Energy and Photon Energies

For hundreds of years, it was generally known that all properties of light could be explained in terms of its wave nature.

However, from investigation by Max Planck and Albert Einstein showed that some phenomena cannot be explained
using a wave model of light.

➢ Blackbody radiation is the emission of light from hot objects.

➢ Photoelectric effect is the emission of electrons from metal surfaces on which light shines.
➢Emission spectra are the emissions of light from electronically excited gas atoms.

Hot Objects and the Quantization of Energy – Max Planck’s investigation

➢ Heated solids emit radiation over a wide range of wavelengths.

➢ Light/color of maximum intensity from a hot solid varies in a specific way with temperature.

➢This is because at given temperature, the atoms in the solid oscillate/vibrate with a definite frequency, .

➢For example, when an iron rod is heated in a furnace, it first turns to dull red and then progressively
becomes more and more red as the temperature approaches 750C.

➢As the iron is heated further, the radiation emitted becomes more yellow and blue and turns white as the
temperature approaches 1200 C. At this temperature the yellow and blue light mixes with red giving white color.
➢In terms of frequency, it means that the frequency of emitted radiation goes from a lower frequency to a
higher frequency as the temperature increases.

➢So the wavelength distribution depends on the temperature.

➢The ideal body, which emits and absorbs radiations of all frequencies, is called a black body and the
radiation emitted by such a body is called black body radiation.

➢Planck investigated black body radiation and proposed since the light/color varies in a specific way with the
temperature and that at a given temperature atoms vibrate at a specific frequency, , then energy can only
be absorbed or released from atoms in certain discrete amounts given by

E = nh where n are whole numbers; 1, 2, 3…….nth

➢ These amounts are called quanta and the numbers symbolized by n are called quantum numbers

➢ With this, Max Planck brought the idea of quantization of energy.

➢A quantum is the smallest amount of energy that can be emitted or absorbed as electromagnetic radiation.
➢ The relationship between energy and frequency is: E = hν. where h is Planck’s constant (6.626 x 10–34 J.s).

The SI unit Joule (J) = 1 Kg.m2/s2

But ν = c/ l, from the frequency and wavelength relationship

So, E = hc/l and is equals the energy of one photon.

➢ This means that energy and wavelength have an inverse relationship.

➢To understand quantization, consider the notes produced by a guitar (continuous) and a piano (quantized).

➢ A guitar can produce any note when the fingers are placed at an appropriate
spot on the bridge.

➢ A piano can only produce notes corresponding to the keys on the keyboard.
The Photoelectric Effect and Photons

➢The photoelectric effect provides evidence for the particle nature of light and for
quantization.

➢ Einstein extended the work of Planck to the structure of light by assuming if the energy of a
vibrating atom was to change from e.g 3hν to 2hν, the change in energy would be hν.

➢ He further proposed that this change in energy hν would be emitted as a quantum

(photons).

➢ A photon is therefore a particle of electromagnetic energy, whose energy E is proportional

to the observed frequency of light.
E = hν.

➢ Shining light on the surface of a metal or another materials can

cause electrons to be ejected from the surface. This process is called
photoelectric effect.
➢ The electrons will only be ejected if the frequency of light/photons exceed a certain
threshold value characteristic of a given metal.

➢ Below the threshold frequency no electrons are ejected regardless of the number of
photons striking the metal.

➢ The minimum energy that a photon can have and still eject an electron from a material in the photoelectric
effect is called work function, expressed in eV. (1 eV = 1.602 x 10-19 J)

➢ Above the threshold frequency, the excess energy appears as kinetic energy of the ejected electrons

➢ Following the conservation of energy principle, the kinetic energy of the ejected electron is given by:

where me is the mass of the electron and v is the

velocity associated with the ejected electron.

➢ This proves that Light has wave-like AND particle-like properties and E = hv shows this duality where E is the
energy of the light particle (photon) and v is the frequency of the wave associated with it.
 Atomic Spectra: Continuous versus Line Spectrum
➢ Light emitted by heated solid e.g filament bulb, can be separated/spread out to a
spectrum that contains light of all wavelengths called continuous spectrum.

➢ However, not all radiations are continuous.

➢Atoms of a heated gas in a partially evacuated tube produces discrete lines of specific
wavelengths. This type of spectrum is called a line spectrum.
➢ Since each line represents a certain wavelength of photons, then the discrete energies corresponding to
these wavelengths can be expressed as E = hc/l

➢Each element has a unique/characteristic line emission spectrum.

➢ The uniqueness of the line emission spectrum is very useful in the chemical analysis particularly the study
of electronic structure to identify unknown atoms.

➢Flame photometry, used to identify group 1 elements is based on line spectrum.

Types of Spectra: Emission and Absorption Spectra

➢There are two kinds of spectra: emission and absorption spectra.

➢ Emission spectrum is the spectrum of radiation emitted by a substance that has absorbed energy.

➢To produce an emission spectrum, energy is supplied to a sample by heating it or irradiating it with a given radiation
and the wavelength (or frequency) of the radiation emitted, as the sample gives up the absorbed energy, is recorded.
➢ To produce absorption spectrum, a continuum of radiation is passed through
a sample which absorbs radiation of certain wavelengths.

➢ The missing wavelength which corresponds to the radiation absorbed by the matter,
leave dark spaces in the bright continuous spectrum.

➢ Absorption spectrum is a photographic negative of emission spectrum.

 Example: Relationship between Energy and Wavelength

Sodium lamps are commonly used to illuminate highways because of their intense yellow-orange emissions
at 589 nm.

a) Calculate the energy , in joules, of one photon of this light

b) Calculate the energy, in kilojoules, of one mole of such photons
c) To sense visible, light the optic nerve needs at least 2.0 x10-17J of energy to trigger impulses that reach
the brain. How many photons of sodium lamp emission are need to “see” the yellow light?

Solution

Use E = hc/l

a) E = hc/l = [(6.626 x10-34J.s)(2.998 x108 m/s)]/589 X 10-9 m = 3.37 x 10-19J

b) E/mol of photons = E = 1 mol photons x (6.022 x 1023 photons/ 1 mol photons) x 3.37 x 10-19 J/ 1 photon x 1KJ/1000 J = 203 Kj

c) # photons = Total E require to trigger impulse divided by energy of one photon = 2.0 x10-17 J x 3.37 x 10-19 J / 1 photon = 59
photons
Theories of the Atomic Structure

➢ After the discovery of the electron but before the discovery of the atomic nucleus, J. J. Thomson in
1904, proposed plum pudding model to explain the structure of an atom.

➢ Thompson used the two properties of atoms that were known then to propose that electrons are surrounded
by a volume of positive charge, like negatively charged "plums" embedded in a positively charged "pudding
and that this leads to a zero charge of the atom. This was disapproved after discovery of the nucleus.

➢On the other hand, Rutherford, in his model, assumed that electrons orbited the nucleus the way planets orbit
the sun.

➢ This assumption was invalid because a charged particle (e.g an electron) moving in a circular path loses energy
in in form electromagnetic radiation.

➢ Adoption this model would mean that the electrons would lose energy and spiral into nuclear thereby leading
to the collapse of the atom. This model therefore could not explain the stability of an atom.
➢From the work of Planck and Einstein and the line spectra of the simplest atom, hydrogen; Bohr
suggested that electrons were confined to specific energy states called orbits and came up with
Bohr’s model

➢ Bohr’s model is based on three postulates:

1 Only orbits of specific radii, corresponding to certain definite energies, are permitted for
electrons in an atom. This means an electron can only have specific energy values in an atom
called energy levels.

2. The energy of an electron in the orbit does not change with time. However, energy changes
when electronic transition occurs i.e an electron moves from a lower stationary state to a
higher stationary state and vice versa.
E = Ef – Ei Eq. 1
3 The frequency of radiation absorbed or emitted when a transition occurs between two
stationary states that differ in energy by ΔE, is given by:

4 The angular momentum of an electron in a given stationary state is expressed as

Where me is the mass of electron, v is

the velocity, n is the orbit in which the electron is revolving, r is the radius of the nth orbit

Implications of this equation:

1. An electron can only move in those orbits for which its angular momentum is
integral multiple of h/2π. This is why only certain fixed orbits/energy levels are
allowed.

2. n is principal quantum number used to number stationary states for an electron

and hence shows increasing orbit size and energy
The Energy States of the Hydrogen Atom (Bohr model)
➢ From Planck’s idea of energy quantization, Bohr expressed the energy of an electron in
its stationary state as:
Eq. 2

Where RH is the Rydberg constant and its value is 2.18 x 10-8 J, n is the Principal quantum number that takes
integral values 1, 2, 3,………..

NOTE:
➢ The negative sign in equation 2 means that the energy of the electron in the atom is lower than the energy of a free
electron at rest.

➢ A free electron at rest is an electron that is infinitely far away from the nucleus and is assigned the energy value of
zero. (doesn’t experience nuclear attraction)

➢ Mathematically, this corresponds to setting where n =  so that E = 0.

➢ As the electron gets closer to the nucleus (as n decreases), En becomes larger in absolute value and more and more
negative.

➢ The most negative energy value is given by n = 1 which corresponds to the most stable orbit. We call this the ground
state.
Line Spectra of the Hydrogen Atom (Bohr model)

➢ Since the energy states are quantized, the light emitted from excited atoms ( e.g hydrogen
atoms) must be quantized and appear as line spectra.

➢ Spectra from excited gases (e.g H2) arise because electrons move between orbits/energy
states/levels in the atom.

➢ The energy gap between two orbits in the hydrogen atom is given by the equation below

NB: This equation is

obtained by combining
Eq1 #2
➢ If this energy is light, for instance, then the frequency (ν) associated with the absorption
and emission of the photon (light is composed of photons) is given by:
Transitions of the electron in the hydrogen atom
Limitations of the Bohr Model

➢ It cannot explain the spectra of atoms other than hydrogen.

➢ Electrons do not move about the nucleus in circular orbits. This would have
meant that they lose energy with time, and if this happens the structure of
the atom should collapse.

➢ It ignores the dual behaviour of matter.

➢ It contradicts Heisenberg uncertainty principle – by assuming circular

orbits.
 Example: Determining the wavelength or frequency of a hydrogen atom transition

What is the wavelength of light emitted when the electron in a hydrogen atom undergoes a transition from energy level
n = 4 to n = 2?

Solution
Remember the wavelength or frequency of a transition depends on the difference in energies of the levels involved,
-E = (Ef – Ei ) = hν Energy of emitted phpton .

Also, energy of an electron in a stationary energy state is given by:

Therefore - = (-RH/22) –(-RH/42) = =(-RH/4) –(-RH/16) = (-4RH + RH)/ 16 = - 3RH/16 = hν

Therefore v = 3RH/16h = 3/16 x (2.179 x 10-18J/6.626 x 10-34 J.s) = 6.17 x 1014/s

But l = c/ν, therefore l = (2.998 x 108m/s)/(6.17 x 1014/s) = 4.86 x 10-7 m or 486 nm

Example: Determining the energy level of a transition in a hydrogen atom transition
Light of 4.08824 x10-19 J is emitted when the electron in a hydrogen atom undergoes a transition from
energy level n = 4 to a lower energy level n = x? What is the value of n for the lower energy level?

Solution
Remember the wavelength or frequency of a transition depends on the difference in energies of the
levels involved,
That is E = Ef – Ei = hν.

Note that since energy is emitted E is negative

Also, energy of an electron in a stationary energy state is given by:

Therefore and

- 4.08824 x10-19 J = 2.179 x 10-18J X(1/42 – 1/X2) = 2.179 x 10-18J X(1/16 – 1/X2)
- 4.08824 x10-19 J = 2.179 x 10-18J X(1/16 – 1/X2)} …………………………………………………….joules cancel
- 4.08824 x10-19/2.179 x 10-18 = {2.179 x 10-18J X(1/16 – 1/X2)}/ 2.179 x 10-18J ……divide through by 2.179 x10-18
0.187620009 = (1/16 – 1/X2)
1/X2 = (1/16 +0.187620009) = 0.250120009 ………………………bring like terms together
X2 =(1/ 0.250120009) = 3.998080774 ………………….find square root of both sides
X = 1.999 = 2
Quantum mechanics: The Wave Behaviour of Matter

➢ Due to the shortcomings of the Bohr’s model, there was need to advance another theory called quantum
mechanics which applies to submicroscopic particles of matter e.g electron.

➢ This theory accounts for wave-particle duality of matter and is consistent with Heisenberg uncertainty
principle

➢ Therefore, principles of quantum theory underpins the current understanding of the atomic structure.

➢ Just as the photon has both the momentum and wavelength, electrons and thus matter do have momentum
as well as wavelength.

➢ Using Einstein’s and Planck’s work and their equations, E = hc/l, E = mc2 and momentum (p) = m x v,
where m is mass, c speed of light and v is velocity.

➢ de Broglie devised an expression that shows both the particle and wave character of an electron and hence
matter. Below is the derivation of de Broglie expression:

Since a photon is a particle of light, then p = mc, where c is speed of light.

But from Einstein mass-energy relation, E = mc2 , therefore mc2 = hc/l = mc = h/l = p.
➢ From the above momentum-wavelength relation for a photon, de Broglie reasoned that particles of matter
exhibit characteristic waves under proper circumstances.

➢ He therefore derived the expression below for the matter called de Broglie relation.

where m is mass and v is velocity of matter

➢ The momentum, mv = p, is a particle property, whereas λ is a wave property.

➢ In this one equation, de Broglie summarized both the concepts of waves and particles as they apply to low
mass, high-speed objects.

➢ Because of de Broglie’s discovery, we now have techniques such as X-ray diffraction and electron microscopy
to study micro and nanoscopic objects.

➢ According to de Broglie, every object in motion has a wave character (also called matter wave)

➢ The wavelengths associated with ordinary (macroscopic) objects are so short (because of their large masses)
that their wave properties cannot be detected.

➢ The wavelengths associated with electrons and other subatomic particles (with very small mass) can however
be detected experimentally.
Quantum mechanics: Wave functions

➢ de Broglie relation only applies to particles in a force-free environment.

➢ Therefore, its drawback is that it cannot be applied to an electron in an atom since the electron is under the influence
of the nuclear force.

➢ Erwin Schrondinger, guided by de Broglie work, devised a theory/model that can be used to find the wave properties of
an electron in atoms and molecules called quantum mechanical model.

➢ The quantum mechanical model/atom differs from the Bohr model/atom in several ways. In particular, based on
quantum mechanics:

1. The kinetic energy of an electron is inversely proportional to the volume of the region to which it is confined.
This phenomenon has no parallel in classical mechanics and explains the stability of the hydrogen atom.
- Based on this proposition, the stability is attained as follows: when an electron comes closer and closer to the nuclear, the electrostatic energy
decreases, i.e becomes more negative. If this were the only factor, the electron would radiate energy and crash into the nucleus. However, the
kinetic energy is increasing as it comes closer because the electron is moving within a smaller and smaller volume. The two effects oppose each
other, a balance is attained, and the atom is stable.

2. It is impossible to specify the precise position of an electron in an atom at a given instant.

- this means that we cannot describe in detail the path/trajectory an electron takes about the nucleus.
- in other words, if we cannot say where the electron is, we certainly cannot know how it got there.
- Therefore, the best we can do is to estimate the probability of finding the electron within a particular region.
The Uncertainty Principle
➢ Because of dual behavior of matter and radiation, uncertainty principle was devised.

➢ Heisenberg uncertainty principle: we cannot determine the exact position, direction of motion, and speed of subatomic
particles simultaneously.

➢ For electrons: we cannot determine their exact momentum/velocity and position simultaneously.

➢ Mathematically, it is a relation which states that the product of the uncertainty in position and the uncertainty in
momentum of a particle can be no smaller than Planck’s constant divided by 4π.

Therefore: Δx * Δpx ≥ h/4π OR Δx * Δ(mvx) ≥ h/4π OR Δx * Δvx ≥ h/4πm

where Δx is the uncertainty in position and Δpx( or Δvx ) is the uncertainty in momentum (or velocity) of
the particle.

Note: only one direction has been considered i.e x. the same can be applied to y and x directions.

The implication of the above expression:

➢ If the position of the electron is known with high degree of accuracy (Δx is small), then the velocity of the electron will
be uncertain, (Δvx) is large AND vice versa.
Significance of Uncertainty Principle

➢It rules out existence of definite paths or trajectories of electrons and other similar
particles/subatomic particles.

➢ Is significant only for motion of microscopic objects and is negligible for that of
macroscopic objects.

➢ The precise statements of the position and momentum of electrons have to be replaced by
the statements of probability.

➢ It leads to the quantum mechanical model of atom and hence orbitals (which
are regions where electrons are more likely to be found)
Example: Determining uncertainty in position and velocity for macroscopic and microscopic object

Bearing ball:

Calculate uncertain in position and velocity for a bearing ball weighing 1 mg.

Solution

Note: 1 J = 1 kg m2 / s2 and 1 Kg = 106 mg

V.X = h/4m = (6.626 x 10-34 kg m2 / s2 .s )/[4 x 3.1416 x 1 mg x ( 10-6Kg / 1 mg)]  10 - 28 m2s-1

This value is extremely small and insignificant. This means that when dealing with macroscopic object, the associated
uncertainties are of NO consequence.

An electron:

Calculate uncertain in position and velocity for a bearing ball weighing 9.11 x 10-31 Kg.

Solution

Note: 1 J = 1 kg m2 / s2 and 1 Kg = 106 mg

V.X = h/4m = (6.626 x 10-34 kg m2 / s2 .s )/[4 x 3.1416 x 9.11 x 10-31 Kg]  10 - 4 m2s-1

This value is relatively large and significant. This means that when dealing with macroscopic object, the associated
uncertainties are of consequence.

➢ This level of uncertainty means that if one tries to find the exact location of the electron, for instance to
an uncertainty of only 10–8 m, then the uncertainty  v in velocity would be:

 v = 10 - 4 m2s-1 / 10–8 m = 104 ms-1

➢ This uncertainty is so large that the classical picture of electrons moving in Bohr’s orbits (fixed) cannot
hold .

➢ Therefore, the precise statements of the position and momentum of electrons have to be replaced by the
statements of probability, that the electron has at a given position and momentum.

➢ This is what happens in the quantum mechanical model of atom.

Quantum Mechanics: Schrödinger Equation and Hamiltonian Operator
➢ Quantum mechanics, conceived by Erwin Schrondinger, is the branch of science that takes into account the
dual behavior of matter.

➢ As such, it deals with the study of the motions of the microscopic objects that have both observable wave
like and particle like properties.

➢ Schrödinger proposed a complex differential equation containing both wave and particle terms.

……. Schrödinger Equation

➢ The first 2 terms on the right side of the equation are quantum mechanical operators.

➢ Each measurable parameter in a physical system is a quantum mechanical operator, and the operator
associated with the system energy is called the Hamiltonian.

➢ In classical mechanics, the system energy can be expressed as the sum of the kinetic and potential energies.

➢ For quantum mechanics, the elements of this energy expression are transformed into the corresponding
quantum mechanical operators – the Hamiltonian operator.
➢ The Hamiltonian contains the operations associated with the kinetic and potential energies and for a particle in one
dimension can be written:

➢ Operating on the wavefunction with the Hamiltonian produces the Schrodinger equation.

➢ In the time independent Schrodinger equation, the operation may produce specific values for the energy called energy
eigenvalues. This operation can be expressed in the form:

where the specific values of energy are called energy eigenvalues and the functions Ψi are called eigenfunctions.

➢ In addition to its role in determining system energies, the Hamiltonian operator generates the time evolution of the
wavefunction in the form:

➢ The full role of the Hamiltonian is shown in the time dependent Shrodinger equation where both its spatial and time
operations manifest themselves.

“YOU WILL COVER TIME DEPENDENT SHRODINGER EQUATION IN 2ND YEAR”

Note: Key features of Schrondinger equation and his quantum mechanical model are:

➢ The Schrödinger equation expresses the wave properties of an electron in an atom.

➢ Solving the equation gives E i.e the allowed energy levels the electron can occupy and the corresponding amplitude (height) 
of the electron wave at various points in space associated with each energy level.

➢ The quantity  is called wave function.

➢ The wave function is a mathematical function whose value depends upon the coordinates of the electron in the atom and does
not carry any physical meaning.

➢ Such wave functions of hydrogen with one electron or multi-electron species are called atomic orbitals.

➢ E  which is the total energy of the system takes into account the kinetic energies of all the sub-atomic particles (electrons,
nuclei), attractive potential between the electrons and nuclei and repulsive potential among the electrons and nuclei
individually.

➢ Quantum mechanical model predict all aspects of the hydrogen atom spectrum including some phenomena that could not be
explained by the Bohr model.

➢ Schrödinger equation cannot be solved exactly for a multi-electron atom. This difficulty can be overcome by using approximate
methods whose calculations can be done with the aid of modern computers.

➢ Approximate method calculations show that orbitals in atoms other than hydrogen do not differ in any radical way from the
hydrogen orbitals.
 ➢ The principal difference lies in the consequence of increased nuclear charge which leads to somewhat contracted orbitals in multi-
electron system.

➢ Unlike orbitals of hydrogen or hydrogen like species, whose energies depend only on the quantum number n, the energies of the
orbitals in multi-electron atoms depend on quantum numbers n and l.

Quantum Mechanics: Wave funtions and Atomic Orbitals

➢ A wave function corresponding to an energy state occupied by electron contains all information about the
electron.

➢ An atomic orbital is the wave function Ψ for an electron in an atom. Whenever an electron is described by a
wave function, we say that the electron occupies that orbital.

➢ The wave function is a mathematical function whose value depends upon the coordinates of the electron in
the atom and does not carry any physical meaning.

➢ The square of the wave function, Ψ2, gives the probability of finding an electron at a particular point within
an atom or probability of finding an electron within a region of space.

➢ The wave function Ψ and its square, Ψ2, have values for all location about a nucleus.
➢ Ψ 2 is therefore electron/probability density for the atom and is always positive.

➢ Ψ2 for an electron in the lowest energy level of the hydrogen atom along a line starting from the nucleus is large
near the nucleus ( r = 0), indicating that the electron is most likely to be found in this region. See figure below.

➢ As the distance from the nucleus increases, Ψ2, decreases dramatically but never goes to zero, meaning that the
probability becomes extremely low at distances away from the nucleus.

➢ This means that an atom does not have a definite boundary as envisaged by Bohr model of atom.
➢ In a shell, the probability of finding an electron is greatest at some distance away from the nucleus since the volume
of a shell gets bigger as the distance from the nucleus increases. See below

➢ Though the probability of finding an electron at a point near the nucleus is high, the volume of any shell is small near
the nucleus and thus the probability is low.

➢ A region of high electron density is one where there is a high probability of finding an electron – This region is called
the atomic orbital.