Modern Concepts of Atomic Structure Democritus Concept of Atom

Is matter continuous or discontinuous? Can you break a matter as long as you want?
 Democritus concept of atom: in fifth century
Would you reach some ultimate particle beyond which further division is impossible?
 Dalton’s Atomic Theory: in 1808 by English scientist J. Dalton
 Discovery of electron: in 1897 by British physicist J. J. Thomson To answer these questions, atomic theory developed. The concept of an atom is
 Determination of electron charge and mass: in 1909 by R. Millikan originated from Greek philosopher Democritus.

 Rutherford’s Atomic Model: in 1911

Democritus studied the nature of matter and the constituents of all the substances.
 Discovery of neutron: in 1932 by English physicist, James Chadwick
He postulated that all matter consists of very small, indivisible particles, which he
named atomos (meaning uncuttable or indivisible).

Dalton’s Atomic Theory 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 (a) According to Dalton’s atomic theory, atoms of the same element are identical, but
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……. 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
 Chemical reaction involves only the separation, combination, or rearrangement of atoms; atoms of element Y is 2:1. Note that a chemical reaction results only in the
it does not result in their creation or destruction
rearrangement of atoms, not in their destruction or creation.
 Discovery of Electron Discovery of Electron
J. J. Thomson used a cathode ray tube and his
knowledge of electromagnetic theory to In some experiments, two electrically
determine the ratio of electric charge to the charged plates and a magnet were added to
mass of an individual electron. Cathode ray the outside of the cathode ray tube. The
tube is a glass tube from which most of the symbols N and S denote the north and south
air has been evacuated. When the two metal poles of the magnet. The cathode rays will
plates are connected to a high-voltage source, strike the end of the tube at A in the presence
the negatively charged plate, called the of a magnetic field, at C in the presence of an
cathode, emits an invisible ray. The cathode electric field, and at B when there are no
ray is drawn to the positively charged plate, external fields present or when the effects of
called the anode, where it passes through a the electric field and magnetic field cancel
hole and continues traveling to the other end each other.
of the tube. When the ray strikes the specially
coated surface, it produces a strong Because the cathode ray is attracted by the plate bearing positive charges and repelled
fluorescence, or bright light. by the plate bearing negative charges, it must consist of negatively charged particles.

Discovery of Electron Determination of charge and mass

 Thomson showed that the characteristics of cathode rays are independent of the  In 1909, US physicist Robert Millikan performed a series of experiments and
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 succeeded in measuring the charge of the electron with great precision. His work
electrons are constituents of all matter. This means that atoms can be divided into proved that the charge on each electron was exactly the same (1.602 X 10-19 C)
smaller substance

 He calculated the ratio of the electric charge (e) to its electron’s mass (me), which  Using this charge value in charge to mass ratio formula, he calculated mass of
is -1.76 X 108 C/g. He could not obtain either charge or the mass
electron, which is 9.109 X 10-28 g

Thomson proposed that an atom could be thought of as

a uniform, positive sphere of matter in which electrons  This mass is more than 1800 times smaller than the mass of the lightest atom
are embedded like raisins in a cake. This is called plum
pudding model hydrogen (1.67 X 10-24 g). This clearly shows that electron is a subatomic particle.
 Rutherford’s Nuclear Model of Atom Rutherford’s Nuclear Model of Atom
Ernest Rutherford studied the effects of bombarding  In separate experiments, it was found that each proton carries the same quantity of
thin gold foil and other metal foils with alpha particles charge as an electron and has a mass of 1.67262 X 10-24 g : about 1840 times the mass
(positively charged) from a radioactive source such as of the oppositely charged electron.
uranium.
 At this stage of investigation, scientists perceived the atom as follows: The mass of a
Rutherford's experiments provided him with two important
nucleus constitutes most of the mass of the entire atom, but the nucleus occupies only
pieces of information:
about 1/1013 of the volume of the atom.
First, most of the alpha particles traveled right through the
foil without being deflected at all. This means that atoms  A typical atomic radius is about 100 pm, whereas the radius of
consist mostly of empty space. an atomic nucleus is only about 5 X 10-3 pm.

Second, a few of the alpha particles (about 1 in 8000) were deflected at very sharp angles. In  Although the protons are confined to the nucleus of the atom,
fact, some reflected completely backwards and were detected next to the gun from which they the electrons are conceived of as being spread out about the
were first produced. This reveals that the positive charge in an atom must all be packed nucleus at some distance from it.
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.

Problems with Rutherford’s Atomic Model Discovery of Neutron

One part of Rutherford's model—the nucleus—has turned out to be correct. However, his Rutherford’s model of atomic structure left one major problem unsolved. It was
placement of electrons created some problems, which he himself recognized. The peculiar known that hydrogen, the simplest atom, contains only one proton and that the
difficulty is that electrons cannot remain stationary in an atom. If they were stationary, they helium atom contains two protons. Therefore, the ratio of the mass of a helium atom
would be attracted to the nucleus and become part of it. to that of a hydrogen atom should be 2:1. (Because electrons are much lighter than
But the electrons could not be spinning around the nucleus either. According to a well- protons, their contribution to atomic mass can be ignored.) In reality, however, the
known law of physics, charged particles (like electrons) that travel through space give off ratio is 4:1. Rutherford and others postulated that there must be another type of
energy. Moving electrons would eventually lose energy, lose speed, and fall into the subatomic particle in the atomic nucleus.
nucleus. Electrons in Rutherford's atom could neither be at rest nor in motion.
The proof was provided by another English physicist, James Chadwick in 1932
 Discovery of Neutron Modern Theory of the Atom
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  Atoms are composed of three main subatomic particles: electron, proton and
neutron
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  Most of the mass of the atom is concentrated in the nucleus of the atom
greater than that of protons.
 The protons and neutrons are located within the nucleus, while the electrons
exist outside of the nucleus
The mystery of the mass ratio could now be explained. In the helium nucleus there are two
 In stable atoms, the number of protons is equal to the number of electrons
protons and two neutrons, but in the hydrogen nucleus there is only one proton and no
neutrons; therefore, the ratio is 4:1.

Cont… We Have Learned

 Democritus concept of atom: in fifth century
 The type of atom is determined by the number of protons it has
 Dalton’s Atomic Theory: in 1808 by English scientist J. Dalton
 The number of protons in an atom is equal to the atomic number
 Discovery of electron: in 1897 by British physicist J. J. Thomson
 The sum of the number of protons and neutrons in a particular atom is
called the atomic mass
 Determination of electron charge and mass: in 1909 by R. Millikan
 Rutherford’s Atomic Model: in 1911
 Valence electrons are the outermost electrons
 Discovery of neutron: in 1932 by English physicist, James Chadwick
 Rutherford’s Nuclear Model of Atom From Classical Physics to Quantum Theory
The new era in physics started in 1900 with a young German physicist named Max
 An atom consists of a nucleus many times smaller than the atom itself, with
Planck.
electrons occupying the remaining space.
While analyzing the data on radiation emitted by solids heated to various
temperatures, Planck discovered that atoms and molecules emit energy only in
 How are the electrons distributed in this space?
certain discrete quantities, or quanta.
 What is the role of electrons in atomic stability, chemical bond formation?
 How many electrons are present in an atom? Physicists had always assumed that energy is continuous and that any amount of
 What energies do individual electrons possess? 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 Properties of Waves

A wave is a continuously repeating change or oscillations in matter or Another important property of waves is their speed, which depends on the type of wave
in a physical field by which energy is transmitted. For example, water and the nature of the medium through which the wave is traveling (for example, air, water,
waves. or a vacuum). The speed ( u ) of a wave is the product of its wavelength and its frequency:

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

frequency. Wavelength (λ) is the distance between identical points
Wavelength is usually expressed in units of meters, centimeters, or nanometers, and
on successive waves. The frequency (ν) is the number of waves
frequency is measured in hertz (Hz) or s-1
that pass through a particular point in 1 second. Amplitude is
the vertical distance from the midline of a wave to the peak or The speed of the light wave in vacuum is a constant and independent of wavelength or
trough. The regular variation of the peaks and troughs enable us to frequency. The speed is 3 X 108 m/s
sense the propagation of the waves.
 Electromagnetic Radiation Various Types of Electromagnetic Radiation
 Electromagnetic radiation is the emission and transmission of
energy in the form of electromagnetic waves.
 According to 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.

Planck’s Quantum Theory Planck’s Quantum Theory

 When solids are heated, they emit electromagnetic radiation over a wide range of  The energy E of a single quantum of energy is given by
wavelengths. Where h is called Planck’s constant and n is the frequency of radiation. The value of
 In 1900, Max Planck found a theoretical formula that exactly describes the intensity of Planck’s constant is 6.63 X 10 -34 J. s. Because n = c/λ , this equation can also be expressed
light of various frequencies emitted by a hot solid at different temperatures. as
 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) According to quantum theory, energy is always emitted in integral multiples of hn ; for

energy only in discrete quantities, like small packages or bundles. Planck gave the name example, hn , 2 hn , 3 hn and so forth, but never, for example, 1.67 hn or 4.98 hn. Therefore,

quantum to the smallest quantity of energy that can be emitted (or absorbed) in the this equation can be again written as E= nhn, n is called quantum number.

form of electromagnetic radiation. 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 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). An apparatus for studying the photoelectric effect. Light

 The photoelectric effect could not be explained by the wave theory of light. Einstein of a certain frequency falls on a clean metal surface.

suggested that a beam of light is really a stream of particles. These particles of light are Ejected electrons are attracted toward the positive

now called photons. Using Planck’s quantum theory of radiation as a starting point, electrode. The flow of electrons is registered by a

Einstein deduced that each photon must possess energy E , given by the equation detecting meter. Light meters used in cameras are based
on photoelectric effect.

 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).

Photoelectric Effect Photoelectric Effect

Removing electron from the metal requires light of a sufficiently high frequency (i.e. sufficiently
Problem: The work function of cesium metal is 3.42 X 10-19 J. (a) Calculate the minimum
high energy) to break them free. Shining a beam of light onto a metal surface can be thought of
frequency of light required to release electrons from the metal. (b) Calculate the kinetic
as shooting a beam of particles—photons—at the metal atoms. If the frequency of photons is
energy of the ejected electron if light of frequency 1.00 X 1015 s-1 is used for irradiating
such that hn is exactly equal to the energy that binds the electrons in the metal, then the light
the metal
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 Strategy: (a) The relationship between the work function of an element and the
energy. This situation is summarized by the equation frequency of light is given by Equation
where KE is the kinetic energy of the ejected electron and W is the work function, which The minimum frequency of light needed to dislodge an electron is the point where the
is a measure of how strongly the electrons are held in the metal. Rewrite the equation as kinetic energy of the ejected electron is zero. (b) Knowing both the work function and
KE = hn – W, it shows that the more energetic the photon (that is, the higher the frequency), the frequency of light, we can solve for the kinetic energy of the ejected electron.
the greater the kinetic energy of the ejected electron
 Photoelectric Effect Bohr’s Atomic Model
Rutherford’s nuclear model of atom could not explain the position of electrons. Niels
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. 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
Therefore, neither the wave nor the particle view alone is a complete description of light. stability of the hydrogen atom and the line spectrum of the atom.

Bohr’s Atomic Model (Postulate - 1) Bohr’s Atomic Model (Postulate - 2)

Energy level postulate: Electron is allowed to occupy only certain orbits of Transition between Energy levels: An electron in an atom can change energy only by going from
specific energies (energy levels). An electron in any of the allowed orbits will one energy level to another energy level. By doing so, the electron undergoes a transition.
not spiral into the nucleus and therefore will not radiate energy. Bohr
attributed the emission of radiation by an energized hydrogen atom to the According to Bohr, the emission of light from an atom occurs by transition of an electron from
electron dropping from a higher-energy allowed orbit to a lower one and higher energy level (initial energy level, Ei) to a lower energy level (final energy level, Ef).
emitting a quantum of energy (a photon) in the form of light. Bohr showed
Because this transition results in the
that the energies that an electron in hydrogen atom can occupy are: emission of a photon of frequency n
and energy hn, we can write,

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, . . . .)
 Emission Spectrum of Hydrogen 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
Figure: The energy levels in the
 In reality, Bohr’s theory accounted for the observed emission spectra of He+ and Li2+ ions,
hydrogen atom and the various
emission series. Each energy as well as that of hydrogen. However, all three systems have one feature in common—
level corresponds to the energy
each contains a single electron. Thus, the Bohr model worked successfully only for the
associated with an allowed
energy state for an orbit, as hydrogen atom and for “hydrogenlike ions”
postulated by Bohr
 It cannot explain why extra lines appear in the hydrogen emission spectrum when a
magnetic field is applied

Defects of Bohr’s Atomic Model Dual Nature of Electron

Why energy of H electron is quantized? Or
1. The Bohr Model provides an incorrect value for the ground state orbital angular
Why electron in a Bohr atom is restricted to orbiting the nucleus at certain fixed distances?
momentum.
In 1924, French Physicist Louis de Broglie reasoned that if light waves can behave like a stream
2. Duel nature of electron and the Heisenberg Uncertainty Principle because it considers
of particles (photons), then perhaps particles such as electrons can possess wave properties.
electrons to have both a known radius and orbit.
De Broglie’s reasoning led to the conclusion that waves can behave like particles and particles
3. No explanation of fine structure-Existence of additional quantum numbers.
can exhibit wavelike properties.
4. It makes poor predictions regarding the spectra of larger atoms.
According to de Broglie, an electron bound to the nucleus behaves like a standing wave
5. The Bohr Model does not explain fine structure and hyperfine structure in spectral lines.
6. No explanation for Zeeman Effect and Stark Effect.
 Dual Nature of Electron Dual Nature of Electron
If an electron behave like a standing wave, the length of the wave must fit the circumference of In 1924, Louis de Broglie reasoned that if light waves can behave like a stream of particles
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.

Dual Nature of Electron Dual Nature of Electron

An electron moving in a closed orbit is considered as a standing wave. Planck’s equation can be Shortly after de Broglie introduced his equation, in 1927 Clinton Davisson and Lester Germer
applied to this electron wave. So, in the United States and G. P. Thomson in England demonstrated that electrons do indeed
E = hν possess wavelike properties. By directing a beam of electrons through a thin piece of gold foil,
From Einstein equation, we have: Thomson obtained a set of concentric rings on a screen, similar to the pattern observed when X
E= mc2 rays (which are waves) were used.
Therefore, mc2 = hν
or, mc = hν/c = h/λ Figure: (a) X-ray diffraction pattern of
aluminum foil. (b) Electron diffraction
Hence, λ = h/mc of aluminum foil. The similarity of
Applying the above equation on electron moving with velocity v and associated with these two patterns shows that
electrons can behave like X rays and
wavelength λ, the de Broglie relationship is obtained as: display wave properties.
l = h/mv,
 Dual Nature of Electron 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,

Dx and Dp are the uncertainties in measuring the position and momentum of the particle,
respectively.

Heisenberg Uncertainty Principle Schrödinger Equation (1926)

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.
m = mass of the electron
But his theory did not provide a complete description of electronic behavior in atoms. E = Total energy of the electron
In 1926 the Austrian physicist Erwin Schrödinger, using a complicated mathematical technique, V = Potential energy of the electron
formulated an equation that describes the behavior and energies of submicroscopic particles in
ψ = Wave function

general.
 Schrödinger Equation (1926) Schrödinger Equation (1926)
Acceptable solutions to the wave equation, that is solutions which are
physically possible, must have certain properties: Several wave functions called ψ1, ψ2, ψ3…. will satisfy these conditions to the
wave equation, and each of these has a corresponding energy E 1, E2 , E3 . ….
1. ψ must be continuous.
2. ψ must be finite. Each of these wave functions ψ1, ψ2 , etc. is called an orbital, by analogy with
3. ψ must be single valued. the orbits in the Bohr theory.
4. The probability of finding the electron over all the space from plus infinity
to minus infinity must be equal to one. In a hydrogen atom, the single electron normally occupies the lowest of the
The probability of finding an electron at a point x, y, z is ψ2, so energy levels E 1. This is called the ground state. The corresponding wave
function ψ1 describes the orbital, that is the volume in space where there is a
high probability of finding the electron.

Schrödinger Equation (1926) Schrödinger Equation

 This equation incorporates both particle behavior, in terms of mass m , and wave behavior,
in terms of a wave function  (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, 2 , gives the probability
of finding the particle within a region of space. Left figure is a representation of the electron density distribution surrounding the nucleus in
 We can obtain the probability of finding an electron at a certain point in a hydrogen atom. the hydrogen atom. It shows a high probability of finding the electron closer to the nucleus.
Although we cannot say that electron will definitely at a particular position at a given time, Right figure shows the probability of finding the electron within shells at various distances from
we can say that the electron is likely to be at this position. 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.
 Schrödinger Equation (1926)
Evolution of atomic model
For a given type of atom, there are a number of solutions to the wave equation
which are acceptable, and 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. Psi is
a function of three quantum numbers

Quantum Numbers Principle Quantum Number (n)

Four quantum numbers: Principal quantum number (n) is the one on which the energy of an electron in an atom
1. Principal quantum number (n) principally depends. It can have integral values 1, 2, 3, and so forth….It corresponds to
2. Angular momentum quantum number (l) the quantum number in the equation:
3. Magnetic quantum number (ml)
4. Spin quantum number (ms)
In a hydrogen atom, the value of n determines the energy of an orbital.
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 principal quantum number also relates to the average distance of the electron from
the Schrödinger equation for the hydrogen atom. Spin quantum number describes the the nucleus in a particular orbital. The larger the n, the greater the average distance of an
behavior of a specific electron and completes the description of electrons in atoms electron in the orbital from the nucleus and therefore the larger the orbital.
 Principle Quantum Number (n) Angular Momentum Quantum Number (l)
It describes the shape of the orbital occupied by the electron. It’s values depend on the
The principal quantum number also relates to the average distance of the electron from
value of the principal quantum number, n . l = 0 to n-1
the nucleus in a particular orbital. The larger the n, the greater the average distance of an
If n=1, there is only one possible value of l; that is, l= n-1 = 0.
electron in the orbital from the nucleus and therefore the larger the orbital.
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.
n=2 n=3
n=1 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) Magnetic quantum number (ml)

The value of l is generally designated by the letters s , p , d, . . . as follows:
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:
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
What is the values of ml if l = 0 or 1 or 2?
When l=2, the orbital is double dumb-bell shaped and is called a d orbital
Consider a situation in which n=2 and l=1. The values of n and l indicate what?
When l=3, a more complicated f orbital is formed
It indicates a 2p subshell, and in this subshell we have three 2p orbitals (because there
The letters s, p, d, f come from the spectroscopic terms sharp, principal, diffuse and
are three values of ml, given by -1, 0 and 1). The orbitals have the same shape but
fundamental, which were used to describe the lines in the atomic spectra.
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 Orbital Groups

Examination of a list of all the allowed solutions to the wave equation shows that the In the second group of solutions to the wave equation, ψ depends both on the distance r

orbitals fall into groups. from the nucleus, and on the direction in space (x, y or z). Orbitals of this kind occurs

In the first group of solutions the value of the wave function ψ, and hence the probability when l=1. These are called p orbitals and there are three possible values of the magnetic

of finding the electron ψ2, depends only on the distance r from the nucleus, and is the quantum number (m = -1, 0, +1). Therefore, there are three orbitals which are identical in

same in all directions. energy, shape and size, which differ only in their direction in space. These three solutions

Ψ = f(r) to the wave equation may be written,

This leads to a spherical orbital and occurs when l=0. These are called s orbital. When l=0, Ψx = f(r) . f(x)

m is also 0. So there is only one such orbital for each value of n. 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 Spin Quantum Number (ms)
In the third group of solutions to the wave equation depends on the distance r from the It refers to the two possible orientation of the spin axis of an electron. The values are
nucleus, and also on two directions in space, for example, +1/2 and -1/2.
Ψ = f(r) . f(x) . f(y) An electron acts as though it were spinning on its axis like the earth. Such an electron
These group of orbitals has l=2. These are called d orbitals. There are five solutions spin would give rise to a circulating electric charge that would generate a magnetic field.
corresponding to m= -2, -1, 0, +1 and +2. These are all equal in energy. Therefore, five In this way, an electron behaves like a small bar magnet, with a north and south pole.
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) Applying the rules for quantum number
The Spin Quantum Number begins with an experiment by Otto Stern and Walther State whether each of the following sets of quantum numbers is permissible for an

Gerlach, which demonstrated that a beam of atoms split evenly into two. This is electron in an atom.

due to a property of the electrons that causes them to generate their own a. n = 1, l = 1, ml = 0, ms = +1/2
b. n = 3, l = 1, ml = -2, ms = -1/2
magnetic field and, consequently, their own internal momentum.
c. n = 2, l = 1, ml = 0, ms = +1/2
d. n = 2, l = 0, ml = 0, ms = 1
 Quantum Mechanical Description of H Atom Quantum Mechanical Description of H Atom
The Schrödinger equation specifies the possible energy states the electron can occupy in a To distinguish the quantum mechanical description of an atom from Bohr’s model, we speak
hydrogen atom and identifies the corresponding wave functions () . These energy states and of an atomic orbital, rather than an orbit.
wave functions are characterized by a set of quantum numbers, with which we can construct a
comprehensive model of the hydrogen atom. 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
The square of the wave function, 2 , defines the distribution of
probability of finding the electrons. Atomic orbital has a definite shape.
electron density in three-dimensional space around the nucleus.
Regions of high electron density represent a high probability of
An atomic orbital, therefore, has a characteristic energy, as well as a characteristic
locating the electron, whereas the opposite holds for regions of
distribution of electron density.
low electron density.

For Multi-electron System Radial and Angular Function

The Schrödinger equation works nicely for the simple hydrogen atom and related ions such as For most calculations, it is simpler to solve the wave equation if the cartesian coordinates x, y
He+ and Li2+, but only approximate solution could be obtained for multi-electron system. and z are converted into polar coordinates r, θ and φ.

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

Fortunately, chemists and physicists have learned to get around this kind of difficulty by
and z in cartesian coordinates, and r, θ and φ in polar
approximation. For example, although the behavior of electrons in multi-electron atoms is
coordinates. The two sets of coordinates are related by the
not the same as in the hydrogen atom, we assume that the difference is probably not too
following expressions:
great. Thus, we can use the energies and wave functions obtained from the hydrogen atom as
Z = r cosθ
good approximations of the behavior of electrons in more complex atoms. In fact, this Figure: The relationship between
Y = r sin θ sin φ cartesian and polar coordinates
approach provides fairly reliable descriptions of electronic behavior in many-electron atoms.
X = r sin θ cos φ
 Radial and Angular Function Radial and Angular Function
The Schrödinger equation is usually written as:

R(r) is a function that depends on the distance from the nucleus, which in turn depends on
where, the quantum numbers n and l.
Θ(θ) is an function of θ, which depends on the quantum numbers l and m
Changing to polar coordinates, becomes
Ф(φ) is a function of φ, which depends only on the quantum number m

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

The solution of this form is,

Radial and Angular Function Electron Probability Density vs. Radial Probability
Probability Density
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.
Figure: Probability of finding the electron
2. Aml, the total angular wave function, which depends on the quantum numbers l and m in the ground state of the hydrogen atom
at different points in space

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.

(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 values of r
is very small but not zero
Electron Probability Density vs. Radial Probability Electron Probability Density vs. Radial Probability
Radial Probability (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
Radial Probability is the probability of finding an electron at a distance r from the nucleus. It can be the dots is therefore greatest in the innermost shells (c) The surface
calculated by adding together the probabilities of an electron being at all points on a series of x area of each shell, given by 4πr2, increases rapidly with increasing r. (d)

spherical shells of radius r1, r2, r3,……, rx-1, rx. 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
we are dividing the atom into very thin concentric surface area of each shell increases more rapidly with increasing r than

shells, much like the layers of an onion, and the electron probability density decreases, a plot of electron probability
versus r (the radial probability) shows a peak at a particular distance.
calculating the probability of finding an electron on
When r is very small, the surface area of a spherical shell is so small that
each spherical shell. Recall that the electron
the total probability of finding an electron close to the nucleus is very
probability density is greatest at r = 0, so the density
low; at the nucleus, the electron probability vanishes because the
of dots is greatest for the smallest spherical shells.
surface area of the shell is zero.

Electron Probability Density vs. Radial Probability Electron Probability Density vs. Radial Probability
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
Probability Densities for the 1s, 2s, and 3s Orbitals of the Hydrogen Atom (a) The electron probability density in
models is attributable to the wavelike behavior of the electron and the Heisenberg any plane that contains the nucleus is shown. Note the presence of circular regions, or nodes, where the probability

Uncertainty Principle. 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.
Electron Probability Density vs. Radial Probability Radial Distribution Functions
Note that all three orbitals are spherically symmetrical. For the 2s and 3s orbitals, For a given value of r the number of

however (and for all other s orbitals as well), the electron probability density does not small volume is 4πr2, so the
probability of the electron being at
fall off smoothly with increasing r. Instead, a series of minima and maxima are
a distance r from the nucleus is 4πr2
observed in the radial probability plots (part (c) in the figure). The minima correspond
R2. This is called the radial
to spherical nodes (regions of zero electron probability), which alternate with
distribution function.
spherical regions of nonzero electron probability.

Figure: Radial distribution function

for various orbitals in the H atom.

Radial Distribution Functions s Orbitals

Three things happen to s orbitals as n increases:
• Radial probability is always small near the nucleus and zero at the nucleus
1. They become larger, extending farther from the nucleus.
• The position of principal maximum depends on n and l values 2. They contain more nodes. This is similar to a standing wave that has regions of significant amplitude
• The most probable distance increases markedly as the principal quantum number separated by nodes, points with zero amplitude.
increases. In other way, for a fixed l, as n increases, the position of principal maximum 3. For a given atom, the s orbitals also become higher in energy as n increases because of their increased
moves to larger r values distance from the nucleus.

• For a fixed n value, the most probable radius decreases slightly as the subsidiary
Orbitals are generally drawn as three-dimensional surfaces that enclose 90% of the electron density, as was
quantum number increases
shown for the hydrogen 1s, 2s, and 3s orbitals. Although such drawings show the relative sizes of the
• No. of radial nodes = n-l-1
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 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.
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.

d 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 3dx2-y2 orbital. The fifth 3d orbital,
called 3dz2 orbital, has a unique shape. It looks like a 2p orbital combined with an additional doughnut
of 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

The surfaces shown enclose 90% of the total electron probability for the five hydrogen 3d orbitals
 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 Orbital Energies

Level Diagram for the Hydrogen Atom (considering atoms or ions with only a single electron). Each box In general, both energy and radius decrease as the nuclear charge increases. As a result of the Z2

corresponds to one orbital. Note that the difference in energy between orbitals decreases rapidly with dependence of energy in energy Equation, electrons in the 1s orbital of carbon, which has a nuclear

increasing values of n. The orbital energies depend on only the principal quantum number n. charge of +6, lie roughly 36 times lower in energy than those in the hydrogen 1s orbital, and the 1s

Consequently, the energies of the 2s and 2p orbitals of hydrogen are the same; the energies of the 3s, orbital of tin, with an atomic number of 50 is roughly 2500 times lower still. The most stable and tightly

3p, and 3d orbitals are the same; and so forth. bound electrons are in orbitals (those with the lowest energy) closest to the nucleus.

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 For example, in the ground state of the hydrogen atom, the single electron is in the 1s orbital, whereas

charge Z (the number of protons in the nucleus): 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,
E = -RH(z2/n2) and all subshells within a principal shell, such as the s, px, py, and pz orbitals, are degenerate.
 Effective Nuclear Charge Effective Nuclear Charge
If an electron is far from the nucleus, then at any given moment, most of the other electrons will
For an atom or an ion with only a single electron, we can calculate the potential energy by
be between that electron and the nucleus. Hence the electrons will cancel a portion of the positive
considering only the electrostatic attraction between the positively charged nucleus and the
charge of the nucleus and thereby decrease the attractive interaction between it and the electron
negatively charged electron. When more than one electron is present, however, the total
farther away. As a result, the electron farther away experiences an effective nuclear charge (Zeff) that
energy of the atom or the ion depends not only on attractive electron-nucleus interactions but
is less than the actual nuclear charge Z. This effect is called electron shielding. If an electron is very
also on repulsive electron-electron interactions. When there are two electrons, the repulsive close to the nucleus, then at any given moment most of the other electrons are farther from the
interactions depend on the positions of both electrons at a given instant, but because we nucleus and do not shield the nuclear charge. At r ≈ 0, the positive charge experienced by an electron is
cannot specify the exact positions of the electrons, it is impossible to exactly calculate the approximately the full nuclear charge, or Zeff ≈ Z. At intermediate values of r, the effective nuclear
repulsive interactions. Consequently, we must use approximate methods to deal with the charge is somewhere between 1 and Z: 1 ≤ Zeff ≤ Z. Thus the actual Zeff experienced by an electron in a

effect of electron-electron repulsions on orbital energies. 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.

Effective Nuclear Charge and Orbital E Effective Nuclear Charge and Orbital E
Although a 2s electron spends most of its time (on average) slightly farther from the nucleus than a
Within a given principal shell of a multielectron atom, the
2p electron, the electron density near the nucleus is actually greater for the 2s electron (see the
orbital energies increase with increasing l. An ns orbital
small maximum for the 2s orbital in Figure). For this reason, the 2s orbital is said to be more
always lies below the corresponding np orbital, which in
“penetrating” than the 2p orbital. Therefore, a 2s electron is less shielded by the 1s electrons and is
turn lies below the nd orbital. These energy differences are
more strongly held by the nucleus. In fact, for the same principal quantum number n , the
caused by the effects of shielding and penetration, the
penetrating power decreases as the angular momentum quantum number / increases, or
extent to which a given orbital lies inside other filled
s>p>d>f>…
orbitals.
Because the stability of an electron is determined by the strength of its attraction to the nucleus, it

For example, an electron in the 2s orbital penetrates inside a filled 1s orbital more than an electron in a 2p orbital does. follows that a 2s electron will be lower in energy than a 2p electron.
Hence in an atom with a filled 1s orbital, the Zeff experienced by a 2s electron is greater than the Zeff experienced by a To put it another way, less energy is required to remove a 2 p electron than a 2 s electron because a
2p electron. Consequently, the 2s electron is more tightly bound to the nucleus and has a lower energy, consistent with 2 p electron is not held quite as strongly by the nucleus. The hydrogen atom has only one electron
the order of energies. and, therefore, is without such a shielding effect.
Energy of the Orbitals Filling of the Orbitals
Figure: Orbital Energy Level Diagram for a Typical Multielectron Atom
Figure: The order in which atomic subshells are
filled in a many-electron atom. Start with the 1s
Because of the effects of shielding and the different radial distributions of
orbital and move downward, following the
orbitals with the same value of n but different values of l, the different
direction of the arrows. Thus, the order goes as
subshells are not degenerate in a multielectron atom. For a given value of follows: 1s , 2s , 2p , 3s , 3p , 4s , 3d , . . . .
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
Because of
is lower in energy than the 3d orbitals for most atoms.