Principles of Chemistry

CHEM 101
Fall 2022

Basit Yameen (PhD)

Associate Professor
Department of Chemistry and Chemical Engineering
SBASSE, LUMS

Lecture 5
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 Recap Hydrogen : Atomic spectrum
Dual nature of light

ℎ ℎ ℎ Continuous spectrum
m= m𝑐 =

𝑝=
𝑐 
apparent mass of a photon

Arthur Compton: Compton effect

Photons do exhibit momentum (mv)
- +

 ’ Discrete Line spectrum

X-rays
-  > ’
Electron
- The Bohr model
• Electron in a hydrogen atom moves around the nucleus only in certain allowed circular orbits (non-radiating).
• Angular momentum (mvr) of electrons could only occur in certain increments. Orbit’s radius and its energy are
quantized.
Light as wave Light as stream of photon • Calculated the radii for the allowed orbits. Bohr’s radius for n = 1 for H atom, a0 = 5.29 × 10−11 m
• Expression for the energy levels available to the electron in the hydrogen atom.

de Broglie’s equation, allows All matter exhibit both

us to calculate the wavelength particulate and wave
for a particle. property.

ℎ ℎ𝑐
ℎ  =
m= = 𝐸photon
v mv
The Bohr model
1. The model correctly fits the quantized energy levels of the hydrogen atom and postulates only certain allowed
circular orbits for the electron.
2. As the electron becomes more tightly bound, its energy becomes more negative relative to the zero-energy
reference state (corresponding to the electron being at infinite distance from the nucleus), as the electron is
brought closer to the nucleus, energy is released from the system.

Related numerical problem(s) solved in the reading material.

The Bohr model

When Bohr’s model was applied to atoms other than hydrogen, it did not work at all.

With definite radius and momentum – violation of Heisenberg uncertainty principle. Bohr’s radius (H atom) =
a0 = 5.29×10−11 m (52.9 pm)

Electrons do not move around the nucleus in circular orbits.

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Heisenberg uncertainty principle

There is a fundamental limitation to just how precisely we can know both the position and momentum of a particle at a given time.

ℎ
𝑥 𝑝 is
4
Uncertainty in Uncertainty in
particle’s position particle’s momentum

more accurately we know a particle’s position, the less accurately

we can know its momentum, and vice versa.

Macroscale objects Vs electrons

It is therefore not appropriate to assume that the electron is moving around

the nucleus in a well-defined orbit, as in the Bohr model (52.9 pm).

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De Broglie’s Hypothesis
Electrons in the hydrogen
“motion of a particle is associated with a atom to be a standing
propagating wave” wave Circumference 2r = n

ℎ ℎ
= 𝑝=
mv 
r
He assigned a frequency not to the particle
but to a wave that accompanies the particle
through space and time in such a way that it
was always in phase with the particle. ℎ
=
mv
- 2𝑟 =
𝑛ℎ
mv
Schrödinger emphasis to the wave
properties of the electron 𝑛ℎ
Schrödinger/De Broglie: Electron mv𝑟 =
2
bound to the nucleus seemed similar to
a standing wave - wave mechanical Angular momentum
description of the atom (mvr) is quantized

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Electrons in Atoms

Precisely know the Can’t precisely Probability

position know the position Spread out over a
region of space.

Both the quantization of energy, and the idea that

we can only talk about the probability of a particle
being at a particular location, are closely related to
the wavefunction ().

Classical Quantum Orbitals – Wavefunctions (, psi)

Particle Wave
1H = 1s1 3Li = 1s2 2s1

Wavefunction ()

Wavefunction is a function of the coordinates (x, y, and z) of the electron’s position in three-dimensional space.

If we know the wavefunction, we can work out the energy of the particle and determine the probability of finding it at a
particular position.

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Wavefunction ()
Function is something which, for given values of the variables, can be evaluated to give a number.
f(x) = x2 –x + 2
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S.No. x x2 f(x) = x2 –x + 2
1 0 0 2 3
2 0.25 0.062 1.81 f(x)
2
3 0.5 0.25 1.75
4 0.75 0.56 1.81 1
5 1 1 2
x
6 1.5 2.25 2.75 0 1 2
7 2 4 4 Plot of f(x) = x2 – x +2 against x
8 3 9 8
f(x,y,z) = ax + by + cz2
Wavefunction () is simply a mathematical function of the relevant variables.
For the electron in hydrogen it would be written as (x, y, z) to indicate that it is a function of x, y and z for the electron. 8
Orbitals, Wavefunction ()

Wavefunctions are called orbitals (1s, 2s, 2p, ……) 1s orbital, 1s atomic orbital and 1s wavefunction

Both Energy and Wavefunctions are the solutions of Schrödinger Wave Equation (SWE)


H  = E Schrödinger Equation

Ĥ (Hamiltonian) represents a set of mathematical instructions called An operator is a mathematical tool that acts on a
an operator. function to produce another function.

Ĥ (Hamiltonian) acts to give back the wavefunction multiplied by the In some special cases the operator give back the
constant E, which represents the total energy of the atom. original function simply multiplied by a constant.
Schrödinger Equation corresponds to such a
special case.
The total energy of the atom = Sum of the potential energy due to the
attraction between the proton and the electron, and the kinetic energy
of the moving electron.

 (x, y, z)
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Wavefunction ()
Probability interpretation of the wavefunction

(x, y, z) Wavefunction at position (x,y,z)

[(x, y, z)]2 Probability of finding electron per unit volume (Probability density)

[(x, y, z)]2 V Probability of being in volume V

z
Probability of being in vol V at (x, y, z) = [(x, y, z)]2  V
prob. Density volume

V

y
x V

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Orbitals – Hydrogen Atom
Behavior of the electron – not the overall motion of whole hydrogen atom
Assumption: Nucleus is stationary and positioned at the origin, and then let the electrons revolve around the nucleus.

Electron is held to the nucleus – electrostatic interaction.

electron r
Potential energy

Nucleus
where r is the distance Coulomb potential spherically symmetric
between the electron
potential energy of the electron The 1s orbital
and the nucleus.
varies as -1/r,
 r 
wavefunctions themselves are not necessarily spherically symmetric and can  1s (r ) = N1s exp − 
depend on both the distance from the nucleus and the direction.  a0 

The 1s orbital, the lowest energy wavefunction, depends only on the distance r between the electron and the nucleus.
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