Dynamics of Chemical Systems-1: Part II

CY-1020 (total credit = 1)

Dr. Surajit Maity

Department of Chemistry
Indian Institute of Technology Hyderabad
surajitmaity@iith.ac.in
 Course Details
AIM: Understanding Atomic and Molecular Structures

What do you learn

 Experiments where classical mechanics fail!!
 The dawn of quantum mechanics
 Postulates of quantum mechanics
 Properties and definition of wave function
 Schrodinger equation
 Some exactly solvable problems and solutions
Textbooks:
1. Physical Chemistry by Peter Atkins and Julio de Paula
2. Quantum Chemistry by Ira N. Levine
3. Physical Chemistry by McQuarrie and Simon
The Classical Theory: A Few Achievements
By 19th Century
 Methods for determining atomic masses
 The periodic table based on Physical and chemical
properties of atoms
 Molecular structure of benzene
 Laws of thermodynamics
 Newtonian mechanics
 Maxwell’s equation for electromagnetic waves

Dmitri Mendeleev

Sir Isaac Newton

 Limitations of Classical Theory

 Blackbody radiation

 Heat capacities of solids at temperatures T→0

 Atomic Spectra

 Photoelectric effect
 Blackbody Radiation
 Any object radiates photons above 0 K
 Radiation wavelength/visible wavelength depends on the
temperature of the object

Heated Metal Blocks Filament

 Blackbody Radiation
Ideal Blackbody?
 Completely absorbs incoming radiations of all frequency
and none is reflected

Conceptual Blackbody

Blackbody Radiation
 Blackbody Radiation: Energy Flux
Stefan-Boltzmann Law
 Total radiation energy (M) at temperature T(K)
M = σ T4
σ = Stefan-Boltzmann Constant = 56.7 × 10-9 W m-2 K-4

Example 1-1: if an object is at 1000 K,

M =56.7*10-9 × 1012 Wm-2 = 5.67 W cm-2 (1m2=10000 cm2)

Example 1-2: Temperature of the Sun’s Photosphere

Energy flux M (average) = 6285 W cm-2 = 6285 0000 W M-2

T4=62850000/ 56.7/10-9 ; T = 5770K

Actual temperature of the sun at the surface is ~5777 K

Blackbody Radiation: Distribution
Wien's Displacement Law
 Radiation from the Sun

18000 K 106 K

Taken from NASA.org

 Blackbody Radiation: Distribution

Classical physics assumed this emission of light was a result of

oscillating electrons and can oscillate equally well at any
frequency
Rayleigh-Jeans Law

A Modified Rayleigh-Jeans Law

Radiated energy density at T K
ρ(λ) =8πκT/λ4 ; k=Boltzmann’s Constant =1.3815E-23 JK-1
 Blackbody Radiation:
Failure of Classical Physics
.
Blackbody Radiation: Distribution
Rayleigh-Jeans Law: Ultraviolet Catastrophe

 At shorter wavelengths, there is a major discrepancy between

the theory and the experiment

This divergence is termed as

Ultraviolet Catastrophe
.
Blackbody Radiation: Planck’s Law
Planck’s Law:
Planck’s hypothesis: The permitted values of
energies are integral multiples of frequencies;
i.e.
E = nhν = nhc/λ; n = 0,1,2,…
Energy is Quantized
Max Planck
Value of ‘h’ (6.626 x 10-34 J s)
was determined by fitting the
experimental curve to the
Planck’s radiation law

Higher energy oscillators (at lower

wavelengths) are less populated.
 Blackbody Radiation: Planck’s Law

Rayleigh-Jeans law from Planck’s formula

.
Blackbody Radiation: Distribution
Modified Planck’s Distribution:
The radiated energy density at T
ρ(λ) = 8πhc/(λ5 (ehc/λkT -1))

Planck’s Distribution
Heat Capacities of Solid
 Heat Capacities of Solid

Cv,m=molar heat capacity

R=Ideal gas constant=8.314 kJmol-1
Na=Avogadro number
Dulong – Petit Law
The molar heat capacity of all solids have nearly
same value of ~25 kJ
Heat Capacities of Solid at T→0
 Heat Capacities of Solid at T→0
Einstein formula: Debye formula
(Averaging of all the frequencies
νD)

The atoms in the crystal oscillate The the vibration of atomic

with a single frequency ν and
invoked the Planck’s hypothesis
that these vibrations have
quantized energies nhν
θE is Einstein temperature,
related to the frequency of
atomic oscillators
lattice (phonon) in a box
θD is Debye temperature,
related to the frequency of
phonon vibrations
At high temperature
Cv=3R
Lattice Vibrations
Atomic Spectra
Atomic Spectra
 Atomic Spectra

Hydrogen atom

Balmer’s Formula 𝟏 𝟏 𝟏
= 𝑹𝑯 𝟐
−
𝝀 𝟐 𝒏𝟐
 Atomic Spectra

Hydrogen atom

Balmer’s Formula 𝟏 𝟏 𝟏
= 𝑹𝑯 𝟐
−
𝝀 𝟐 𝒏𝟐

𝑹𝑯 = Rydberg Constant=109678 cm-1

Transition
3→2 4→2 5→2 6→2
of n
nm 656.5 486.3 434.2 410.2
Color Red Aqua Blue Violet
 Atomic Spectra
Hydrogen atom: All the lines in the atomic hydrogen spectrum

Lyman Series Balmer Paschen Series

n1=1 n1=2 n1=3

Rydberg Formula: For all combinations

𝟏 𝟏 𝟏
= 𝑹𝑯 𝟐 − ; n2>n1
𝝀 𝒏𝟏 𝒏𝟐𝟐

𝑹𝑯 = Rydberg Constant=109678 cm-1

Atomic Structure Model
Rutherford Model (1911)
 Bohr Model of Hydrogen Atom
 Electrons rotate in circular orbits around a central (massive)
nucleus, and obeys the laws of classical mechanics.

 Allowed orbits are those for which the electron’s angular

momentum equals an integral multiple of h/2π i.e. mevr =nh/2π

 Energy of H-atom can only take certain discrete values:

“Stationary States”; The Atom in a stationary state does not
emit electromagnetic radiation.

 When an atom makes a transition from one stationary state of

energy Ea to another of energy Eb, it emits or absorbs a photon
of light: Ea–Eb = hv
 Bohr Model of Hydrogen Atom
 Electrons rotate in circular orbits around a central (massive)
nucleus, and obeys the laws of classical mechanics.

 Allowed orbits are those for which the electron’s angular

momentum equals an integral multiple of h/2π i.e. mevr =nh/2π

 Energy of H-atom can only take certain discrete values:

“Stationary States”; The Atom in a stationary state does not
emit electromagnetic radiation

 When an atom makes a transition from one stationary state of

energy Ea to another of energy Eb, it emits or absorbs a photon
of light: Ea–Eb = hv
Bohr Model of Hydrogen Atom

 Angular momentum
quantized
mvr=nh/2π, n=1, 2, 3…

𝒎𝒆 𝒆𝟒 𝟏
 Energy En=- 𝟐 𝟐 𝟐
𝟖𝜺𝟎 𝒉 𝒏

𝒎𝒆 𝒆𝟒 𝟏 𝟏
 ΔEn= 𝟐 𝟐 ( - )
𝟖𝜺𝟎 𝒉 𝒏𝟏𝟐 𝒏𝟐𝟐

𝒎𝒆 𝒆𝟒
 R∞ = equal to
𝟖𝜺𝟐𝟎 𝒄𝒉𝟑
Rydberg constant
 Bohr Theory
For an hydrogen atom

ℎ 𝒏𝒉
 Combining 𝜆 = and 2πr=nλ  𝒎𝒆 𝒗𝒓 =
𝑚𝑣 𝟐𝝅
Angular momentum is quantized and integral multiples of
ℎ
𝑜𝑟 ħ
2𝜋
𝑚𝑒 𝑣 2
 Centrifugal force ( ) is equal to coulombic force
𝑟
𝑒2 𝑚𝑒 𝑣 2
=
4𝜋𝜀0 𝑟 2 𝑟
𝑛ℎ 𝑒2 𝑚𝑒 𝑣 2 𝟒𝝅𝜺𝟎 ħ𝟐 𝒏𝟐
 Put 𝑣 = in = to obtain 𝒓=
2𝜋𝑚𝑒 𝑟 4𝜋𝜀0 𝑟 2 𝑟 𝒎𝒆 𝒆𝟐
 Calculate the smallest radius (when n=1) is r=a0=52.92 pm
 Bohr Theory
For an hydrogen atom

𝒆𝟐
 Potential energy from Coulomb's law V(r)= − . The “–”
𝟒𝝅𝜺𝟎 𝒓
sign indicate attractive interaction.
𝟏 𝟐 𝒆𝟐
 Total energy E=KE +PE= 𝒎𝒆 𝒗 −
𝟐 𝟒𝝅𝜺𝟎 𝒓
2 𝑒2 𝑚𝑒 𝑣 2 𝟏 𝒆𝟐 𝒆𝟐 𝒆𝟐
 (𝑚𝑒 𝑣 from = ); E= ( )− =−
4𝜋𝜀0 𝑟 2 𝑟 𝟐 𝟒𝝅𝜺𝟎 𝒓 𝟒𝝅𝜺𝟎 𝒓 𝟖𝝅𝜺𝟎 𝒓

4𝜋𝜀0 ħ2 𝑛2 𝒆𝟐 𝑚𝑒 𝑒 4
 Use 𝑟= ; En=− = ; n=1, 2, 3,…….
𝑚𝑒 𝑒 2 𝟖𝝅𝜺𝟎 𝒓 8𝜀02 ℎ2 𝑛2
 Derive Rydberg formula from Bohr Theory

 For the ground state n=1, for excited states n=2,3,4...

 Excited states of n2>1 radiates photons during transition to
lower electronic state n1 which is <n2 and
𝑚𝑒 𝑒 4 1 1
E2-E1=hν= 2 2 ( 2 − 2 )
8𝜀0 ℎ 𝑛1 𝑛2
ℎ𝑐 1 𝑚𝑒 𝑒 4 1 1 1 1
 Replace ν= ; = 2 3 2 − = R∞( − ) in cm-1
𝜆 𝜆 8𝜀0 𝑐ℎ 𝑛1 𝑛22 𝑛12 𝑛22
 This equation is similar to the Rydberg formula and the
derived value of R∞ is very similar to the Rydberg constant.

 Calculate R∞ and find out the difference between RH and R∞ in cm-1

 Rydberg formula V/S Bohr Theory
4𝜋𝜀0 ħ2 𝑛2 𝒆𝟐 𝑚𝑒 𝑒 4
𝑟= ; En=− = ; n=1, 2, 3,…….
𝑚𝑒 𝑒 2 𝟖𝝅𝜺𝟎 𝒓 8𝜀02 ℎ2 𝑛2
 Rydberg formula V/S Bohr Theory

Johannes Rydberg Niels Bohr

𝟏 𝟏 𝟏
= 𝑹𝑯 − ; n2>n1
𝝀 𝒏𝟐𝟏 𝒏𝟐𝟐  Circular orbits around a
central (massive) nucleus
𝑹𝑯 = 109678 cm-1
 mevr =nh/2π
 The Atom in a stationary state
does not emit electromagnetic
radiation
 Ea–Eb = hv
 Derive Ionization Energy from Bohr Theory

 Ionization energy= energy required for the ground state

electron to reach an unbound state (energy required to create
H+ from H)
for this, n2= ∞ and n1=1; I.E.= R∞ in cm-1
I.E (in J)=hcR∞; (in J mol-1)= hcNaR∞
 Lecture 2:
Photoelectric effect: Wave-particle Duality
According to Classical Physics:
 Electromagnetic Radiation
Experimental observation
E=E0Sin(kx-t)
 Wave energy is related to
Intensity, I ∝ E02
 With an increase in intensity,
electrons oscillate more
violently, and eventually eject
from the surface
 Kinetic energy of electrons
depend on the intensity of the
radiation but not frequency of
incident radiation
 Photoelectric effect: Wave-particle Duality

 Radiation causes photoelectron Experimental observation

above certain frequency
 Increase in light intensity
increases the number of
photoelectrons, but not their
maximum kinetic energy!
 Weak violet light will eject only a
few electrons! But their
maximum kinetic energies are
greater than those for very
intense light of longer (red)
wavelengths
 Photoelectric effect: Wave-particle Duality

Einstein applied Planck’s idea that

∆E=hν and proposed that radiation
itself existed as small packets of energy
(Quanta) and now known as
PHOTONS

Ep=hν; Energy is frequency dependent

Ep=hν=KEe + φ
φ = work function; Energy required to
remove electron from surface=hν0

KE=h(ν-ν0)

Is photon a particle?
Photoelectric effect: Wave-particle Duality

 The photoelectric effect provides evidence for the

particle nature of light.
 It also provides evidence for quantization.
 If light shines on the surface of a metal, there is a
point at which electrons are ejected from the metal.
 The electrons will only be ejected once the threshold
frequency is reached .
 Below the threshold frequency, no electrons are
ejected.
 Above the threshold frequency, the number of
electrons ejected depend on the intensity of the
light.
 Wave-particle Duality
Diffraction of Electrons
Davisson-Germer Experiment
A beam of electrons is directed onto
the surface of a nickel crystal.
Electrons are scattered, and are
detected by means of a detector that
can be rotated through an angle θ.
When the Bragg condition
mλ = 2dsinθ was satisfied (d is the
distance between the nickel atom, and
m an integer) constructive
interference produced peaks of high
intensity

Is electron a wave?
 Wave-particle Duality

Light can be Waves or Particles

Electron (matter) can be particles or waves

For photons (m=0), change in wavelength results a change in

momentum

de Broglie Hypothesis: wave-particle duality of light (1924)

De Broglie wavelength λ = h/p; p is momentum

 Wave-particle Duality

De Broglie wavelength λ = h/p; p= mv= momentum

 Bohr - de Broglie Theory
For an hydrogen atom

ℎ 𝒏𝒉
 Combining 𝜆 = and 2πr=nλ  𝒎𝒆 𝒗𝒓 =
𝑚𝑣 𝟐𝝅
Angular momentum is quantized and integral multiples of
ℎ
𝑜𝑟 ħ
2𝜋
 Energy Conversion
1 27.21139 219474.63 627.503 2625.438228

hartree eV cm-1 kcal/mol kJ/mol k

hartree 1 27.21139 219474.63 627.503 2625.438228

eV 0.036749322 1 8065.544 23.06031 96.4830761

cm-1 4.55634E-06 0.000124 1 0.002859 0.011962377

kcal/mol 0.001593618 0.043365 349.7587 1 4.183945301

kJ/mol 0.000380889 0.010365 83.595428 0.239009 1

k 3.16679E-06 8.62E-05 0.6950305 0.001987 0.008314216

J 2.29E+17 6.24E+18 5.03E+22 1.44E+20 6.02E+20

Hz 1.52E-16 4.14E-15 3.34E-11 9.54E-14 3.99E-13

nm 45.56335253 1239.842 10000000 28591.14 119623.7675

 Uncertainty Principle

How to understand wave/particle duality:

a) a wave with a definite frequency and wavelength (e.g.,
a nice sine wave) does not have a definite location.
[At a definite location at a specific time the wave would
have a definite phase, but the wave would not be said
to be located there.]
[ a nice travelling sine wave = A sin(kx-ωt) ]

de Broglie Hypothesis, λ = h/p;

momentum is precisely determined
 Uncertainty Principle

b) A particle does have a definite location at a specific

time, but it does not have a frequency or wavelength.
c) In-between case: a group of sine waves can add
together (via Fourier analysis) to give a semi-definite
location: a result of Fourier analysis is this: the more
the group shows up as a spike, the more waves it
takes to make the group.

To know the location of a

particle with some
degree of certainty, we
sacrificed the certainty of
momentum
 Uncertainty Principle

Thus the Heisenberg’s Uncertainty Principle

Position and Momentum: x ⨯ px ≥ h/4

A generalized form of the uncertainty

Principle:
 Uncertainty in Time and Energy

T1/2= half life = Δt= 1 ns; Find out the spectral line
width:
Δt*ΔE = h/4; => Δt*h Δν=h/4π;
=> Δν=1/(4π* Δt)~80MHz~0.003 cm-1
But if an electron acts as a wave when it is moving,
WHAT IS WAVING?

When light acts as a wave when it is moving, we have

identified the ELECTROMAGNETIC FIELD as waving.
We have laws governing the electric and magnetic fields:
MAXWELL’S EQUATIONS.

Classical Mechanics takes care of a particle’s motion.

But what do we do for electron waves (wavy particle)?

New theory is required to explain the behavior of electrons,
atoms and molecules

Should be Probabilistic, not deterministic (non-Newtonian) in

nature

Wavelike equation for describing sub/atomic systems

Operators
A symbol that tells you to do something to whatever follows it
 Operations might be simple multiplication or differentiation
Operators can be real or complex
Operators can also be represented as matrices
 An operator is an instruction, a symbol which tells us to
perform one of more mathematical acts on a function, say f(x).
The essential fact is that they act on a function
 Operator act on everything to the right, unless the action is
constrained by brackets
 Linear Operator

 Here a and b are constants, f and g are functions

 Multiplication is a linear operation; so is differentiation and
integration.
 An example of a nonlinear operation is that of taking the
logarithm of a function
 Linear combination of degenerate wavefunctions is also an
Eigen function
 Linear combinations:

 Degenerate wavefunctions:
 Linear combination of degenerate wavefunctions is also an
Eigen function
 In general, Â1 Â2  Â2 Â1 : Â1 operates on Â2 is not equal to Â2
operates on Â1
 For example, x and px () are position and momentum
operators and x px  px x; check for a specific function x2

 Two operators commute if they obey the simple operator

expression: [Â1 , Â2]= Â1 Â2 - Â2 Â1 = 0 => Â1 Â2= Â2 Â1
On information about a state
On the selection of operators:
Now we compute two ways.

If then
Link between wavefunction/operators with the experimental
observations
Normalization of Wavefunction
Venue: Auditorium & LH-2

Time and Date: 5th Feb (Mon) from 9.45-

11.00 am
Schrödinger’s Wave Equation
 The Potential Energy Function

The potential energy of interaction between a proton and

an electron is described by the equation V(r) = -e2/4e0r

V(r) is zero when the proton and electron are an infinite distance
apart, but is negative at all values of r < . That is, the potential
energy of the electron bound to the nucleus is lower than that of
a free electron.
0
0 1 2 3 4 5
-1E-18

-2E-18

V(r) (J) -3E-18

-4E-18

-5E-18

-6E-18

-7E-18
Time-dependent Schrodinger Equation
Time-dependent Schrodinger Equation
 Examples of Exactly Solvable Systems

Time Independent Schrodinger Equation

1. Free Particle
2. Particle in a 1D/2D/3D box
 Free Particle

Schrodinger Equation

Free Particle: V(x) = 0; No external forces

m x
 Free Particle
m x

Free Particle: V(x) = 0; No external forces

Second-order linear differential equation

Try with a trial solution:

(x) = A sinkx+ B coskx
 Free Particle

Try with a trial solution:

(x) = A sinkx+ B coskx

Eigenvalue function and eigenvalue?

 Free Particle

Try with a trial solution:

(x) = A sinkx+ B coskx

Solution: Energy and Wavefunction

There are no restrictions on k and E can have any value

Energies of free particles are continuous
No quantization, all energies are allowed
 Free Particle

Try with a trial solution:

(x) = A sinkx+ B coskx

Solution: Energy and Wavefunction

(x) = A sinkx+ B coskx

No quantization, all energies are allowed
Particle in an one dimensional box

V(x) = 0 when 0≤x≤L

= ∞ at any other values of x
 Particle in an one dimensional box

V(x) = 0 when 0≤x≤L

= ∞ at any other values of x

Normalization condition not satisfied

(x<0) = 0; (x>L) = 0
 Particle in an one dimensional box

V(x) = 0 when 0≤x≤L

Try with a trial solution:

(x) = A sinkx+ B coskx
 Particle in an one dimensional box

V(x) = 0 when 0≤x≤L

 Particle in an one dimensional box

V(x) = 0 when 0≤x≤L

Wavefunction

Energy
Particle in an one dimensional box

6 36
11
5 25
9  Energy is no longer
4 16 continuous but has
7 discrete values;
3 9  Quantization of
5 energy
2 4  Energy separation
3
1 1 increases with
increasing values of
n En ΔE
n
/(h2/8mL2)
Particle in an one dimensional box

Spectroscopy:
Particle in an 1D box: Wavefunction

Values of A:
𝒏𝝅
(x) = A sin x
𝑳
Normalization Condition

𝑳 𝑳
𝒏𝝅
න ∗(x)(x) . 𝒅𝒙 = 𝑨𝟐 න sin2 x . 𝒅𝒙 = 𝟏
𝟎 𝟎 𝑳
𝑳
𝒙 𝟏
න sin2kx . 𝒅𝒙 =[ − 𝑺𝒊𝒏 𝟐𝒌𝒙 ] 𝑳𝟎
𝟎 𝟐 𝟒𝒌
𝑳
=
𝟐
𝑳 𝟐
So, 𝑨𝟐 . = 𝟏; |𝑨| =
𝟐 𝑳
 Particle in an 1D box: Wavefunction

𝟐
𝑨=± ,
𝑳
A need not to be real, it could be complex
We could use any complex number with
𝟐 𝟐
absolute value of like A= 𝒆𝒊∝
𝑳 𝑳
where ∝ is phase of A.
Considering zero phase of A,

𝟐 𝒏𝝅
(x) = sin x; n=1,2,3,4….
𝑳 𝑳
Particle in an 1D box: Wavefunction

𝟐 𝟒𝝅
(x) = sin x; n=4;
𝑳 𝑳
peaks@ x=L/8, 3L/8, 5L/8, 7L/8
𝟐 𝟑𝝅
(x) = sin x; n=3;
𝑳 𝑳
peaks@ x=L/6, L/2, 5L/6

𝟐 𝟐𝝅
(x) = sin x; n=2;
𝑳 𝑳
peaks@ x=L/4, 3L/4

𝟐 𝝅
(x) = sin x; n=1; peak@ x=L/2
𝑳 𝑳
L
Particle in an 1D box: Wavefunction

Probability |(x)|2
L
Expectation values: Position
Expectation values: Momentum
 Application in Chemistry
6 36 Hexatriene is a linear molecule of
length 7.3 Å. It absorbs at 258 nm
Use particle in a box model to
5 25 explain the results

4 16
𝒉𝟐 𝟐 𝟐 𝒉𝒄
3 9 ∆𝑬 = 𝟐
(𝒏𝒇 −𝒏𝒊 ) =
𝟖𝒎𝑳 𝝀
M=mass of electron; L=length of
2 4 the molecule
1 1
1758
Six π electron fill 𝝀= 𝟐 𝟐 nm
(𝒏𝒇 −𝒏𝒊 )
lower three levels
𝝀 = 251 nm
Application in Chemistry

𝒉𝟐 𝟐 𝟐 𝒉𝒄
𝟐
(𝒏𝒇 −𝒏𝒊 ) =
𝟖𝒎𝑳 𝝀
Particle in an 2D box
Particle in an 2D box
Particle in an 2D box: Square
 Particle in an 2D box: Square

E1,2 = E2,1; 1,2 and 2,1 are degenerate wavefunction

Particle in an 2D box Symmetry/Energy

Lx=2Ly

10 9.25

6.25
5 (4,1)
8 4.25
3.25
5 2
1 1.25
Particle in an 2D box: Wavefunction
Particle in an 3D box
 Tutorial

Physical Constants
Tutorial
Tutorial
Limitations of Bohr’s theory:
(i) It does not explain the spectra of atoms having more than one
electron.

(ii) Bohr’s atomic model failed to account for the effect of

magnetic field (Zeeman effect) or electric field (Stark effect) on
the spectra of atoms or ions.
It was observed that when the source of a spectrum is placed in a
strong magnetic or electric field, each spectral line further splits
into a number of lines. This observation could not be explained
on the basis of Bohr’s model.

(iii) De Broglie suggested that electrons like light have dual

character. It has particle and wave character. Bohr treated the
electron only as particle.
Limitations of Bohr’s theory:
(i) It does not explain the spectra of atoms having more than one electron.
(ii) Bohr’s atomic model failed to account for the effect of magnetic field (Zeeman effect) or
electric field (Stark effect) on the spectra of atoms or ions.
(iii) De Broglie suggested that electrons like light have dual character. It has particle and wave
character. Bohr treated the electron only as particle.

(iv) Another objection to Bohr’s theory came from Heisenberg’s

Uncertainty Principle.

According to this principle “It is impossible to determine

simultaneously the exact position and momentum of a small
moving particle like an electron”.
The postulate of Bohr, that electrons revolve in well-defined
orbits around the nucleus with well-defined velocities is thus not
tenable.
For an hydrogen atom

ℎ 𝒏𝒉
 Combining 𝜆 = and 2πr=nλ  𝒎𝒆 𝒗𝒓 =
𝑚𝑣 𝟐𝝅
Angular momentum is quantized and integral multiples of
ℎ
𝑜𝑟 ħ
2𝜋
𝑚𝑒 𝑣 2
 Centrifugal force ( ) is equal to coulombic force
𝑟
𝑒2 𝑚𝑒 𝑣 2
=
4𝜋𝜀0 𝑟 2 𝑟
𝑛ℎ 𝑒2 𝑚𝑒 𝑣 2 𝟒𝝅𝜺𝟎 ħ𝟐 𝒏𝟐
 Put 𝑣 = in = to obtain 𝒓=
2𝜋𝑚𝑒 𝑟 4𝜋𝜀0 𝑟 2 𝑟 𝒎𝒆 𝒆𝟐
 Calculate the smallest radius (when n=1) is r=a0=52.92 pm
For an hydrogen atom

𝒆𝟐
 Potential energy from Coulomb's law V(r)= − . The “–”
𝟒𝝅𝜺𝟎 𝒓
sign indicate attractive interaction.
𝟏 𝟐 𝒆𝟐
 Total energy E=KE +PE= 𝒎𝒆 𝒗 −
𝟐 𝟒𝝅𝜺𝟎 𝒓
2 𝑒2 𝑚𝑒 𝑣 2 𝟏 𝒆𝟐 𝒆𝟐 𝒆𝟐
 (𝑚𝑒 𝑣 from = ); E= ( )− =−
4𝜋𝜀0 𝑟 2 𝑟 𝟐 𝟒𝝅𝜺𝟎 𝒓 𝟒𝝅𝜺𝟎 𝒓 𝟖𝝅𝜺𝟎 𝒓

4𝜋𝜀0 ħ2 𝑛2 𝒆𝟐 𝑚𝑒 𝑒 4
 Use 𝑟= ; En=− = ; n=1, 2, 3,…….
𝑚𝑒 𝑒 2 𝟖𝝅𝜺𝟎 𝒓 8𝜀02 ℎ2 𝑛2
For an hydrogen atom

𝒆𝟐
 Potential energy from Coulomb's law V(r)= − . The “–”
𝟒𝝅𝜺𝟎 𝒓
sign indicate attractive interaction.
𝟏 𝟐 𝒆𝟐
 Total energy E=KE +PE= 𝒎𝒆 𝒗 −
𝟐 𝟒𝝅𝜺𝟎 𝒓
2 𝑒2 𝑚𝑒 𝑣 2 𝟏 𝒆𝟐 𝒆𝟐 𝒆𝟐
 (𝑚𝑒 𝑣 from = ); E= ( )− =−
4𝜋𝜀0 𝑟 2 𝑟 𝟐 𝟒𝝅𝜺𝟎 𝒓 𝟒𝝅𝜺𝟎 𝒓 𝟖𝝅𝜺𝟎 𝒓

4𝜋𝜀0 ħ2 𝑛2 𝒆𝟐 𝑚𝑒 𝑒 4
 Use 𝑟= ; En=− = ; n=1, 2, 3,…….
𝑚𝑒 𝑒 2 𝟖𝝅𝜺𝟎 𝒓 8𝜀02 ℎ2 𝑛2
 Tutorial

For an He+atom

𝟐𝒆𝟐
 Potential energy from Coulomb's law V(r)= − . The “–”
𝟒𝝅𝜺𝟎 𝒓
sign indicate attractive interaction.
𝟏 𝟐 𝟐𝒆𝟐
 Total energy E=KE +PE= 𝒎𝒆 𝒗 −
𝟐 𝟒𝝅𝜺𝟎 𝒓
2 2𝑒 2 𝑚𝑒 𝑣 2 𝟏 𝟐𝒆𝟐 𝟐𝒆𝟐 𝟐𝒆𝟐
 (𝑚𝑒 𝑣 from = ); E= ( )− =−
4𝜋𝜀0 𝑟 2 𝑟 𝟐 𝟒𝝅𝜺𝟎 𝒓 𝟒𝝅𝜺𝟎 𝒓 𝟖𝝅𝜺𝟎 𝒓

4𝜋𝜀0 ħ2 𝑛2 𝟐𝒆𝟐 2𝑚𝑒 𝑒 4

 Use 𝑟= ; En=− = ; n=1, 2, 3,…….
2𝑚𝑒 𝑒 2 𝟖𝝅𝜺𝟎 𝒓 8𝜀02 ℎ2 𝑛2
 Tutorial

1 2𝑚𝑒 𝑒 4 1 1 1 1
 = 2 3 2− 2 = 2R∞( 2 − ) in cm-1
𝜆 8𝜀0 𝑐ℎ 𝑛1 𝑛2 𝑛1 𝑛22
1
 n2=∞, n1=1. = 2R∞ cm-1
𝜆
 Tutorial

7, 8(a), 9

De Broglie wavelength λ = h/p;

p= mv= momentum
λ=wavelength

8(b) mv2/2 = eΔV

 Tutorial

De Broglie wavelength Uncertainty Principle

λ = h/p; Position and Momentum: x * p ≥ /2.
Time and Energy: Δ t*ΔE ≥ /2
Tutorial