CHM112
Quantum Theory
AGENDA 1 Black-Body Radiation
2 Atomic Models
3 Particle vs Wave Nature
4 The Postulates of QM
Exploring various systems:
5 Free Particle, Particle in
1D, 2D, 3D Box, Quantum
Harmonic Oscillator
BLACK-BODY RADIATION
A body that absorbs and emits radiation at all frequencies
is called a black-body.
A black body has 100% absorbivity. Radiation reaches
thermal equilibrium with black-body temperature.
Each black body at temperature T shows a specific spectral
distribution Eλ. Eλ is the energy density between the range
λ and λ+dλ.
Spectrum DOES NOT depend on material of body.
Intensity of radiation is proportional to volume of cavity.
The graph shown on the right side shows this Eλ plotted
against λ for three different temperatures.
THE BLACK-BODY RADIATION TIMELINE
1860 1879 1884 1896 1900
LUDWIG RAYLEIGH-
KIRSCHOFF LAW JOSEF STEFAN WILHELM WIEN
BOLTZMANN JEANS
At a given T and λ, Relation between Boltzmann provided Gave radiation law for Proposed this equation.
[Emissive power (Wλ)/ Radiance (R) of a black the theoretical proof of spectral energy
Absorptivity(Aλ)] is body (Energy emitted Stefan law distribution-
independent of per unit area per unit where the constant of
substance. second) and its proportionality σ is
absolute temperature. known as Stefan-
Predicted LONG
Boltzmann constant, This got experimentally wavelength behavior
having value 5.67 x verified for SHORT fairly well but failed at
10^-8 J m^-2 s^-1 K^-4. wavelengths but not SHORT wavelength
for LONG wavelengths. causing “ultraviolet
catastrophe”.
PLANCK’S Planck proposed the following:
RADIATION Energy density between v and v + dv =
average energy of each resonator (U) x no.
LAW of resonators per unit volume in the
frequency range v and v + dv
No. of resonators, nv with energy, hv:
Average energy of each resonator:
Energy density in the range v and v+dv:
PLANCK’S RADIATION LAW:
QUESTION
TIME
Consider a black body of volume 100cm^3 at a
QUESTION
temperature of 300K. Estimate the number of
photons in the cavity with wavelengths in the
range 400 to 405nm.
NOTE: In Planck’s Radiation formula, we use dv and not dλ. HOWEVER, everything here
is in terms of λ. DO NOT FORGET TO CHANGE THIS.
ANSWER
QUESTION
TIME
WHICH LAW DESCRIBES THE RELATIONSHIP
QUESTION
BETWEEN THE TEMPERATURE OF A BLACKBODY
AND THE PEAK WAVELENGTH OF ITS EMITTED
RADIATION?
A) PLANCK’S LAW
OPTIONS
B) WIEN’S DISPLACEMENT LAW
C) STEFAN-BOLTZMANN LAW
D) KIRCHOFF’S LAW
ANSWER
B) WIEN’S DISPLACEMENT LAW
THE ONSET OF
QUANTUM
MECHANICS
SOME BASIC POSTULATES OF QM
1 The state of a quantum mechanical system (e.g. an electron) at position r and time t is
completely and uniquely specified by a “wave function” Ψ(rt).
PROBABILITY OF FINDING A PARTICLE IN A
CERTAIN REGION(BORN RULE)
PROBABILITY DENSITY OF FINDING THE PARTICLE/
NORMALISATION OF THE WAVEFUNCTION
NOTE: Ψ* is the complex conjugate of Ψ (that is wherever you see i, you gotta take -i)
2 To every observable/dynamical variable in Classical Mechanics there is a linear, Hermitian
operator in Quantum Mechanics.
THERE EXIST SOME QM OPERATORS FOR CLASSICAL DYNAMICAL VARIABLES-.
CONDITION FOR LINEAR OPERATORS:
Example for linear operator: d/dx
Example for non-linear operator:
2 To every observable/dynamical variable in Classical Mechanics there is a linear, Hermitian
operator in Quantum Mechanics.
HERMITIAN OPERATORS ARE OPERATORS THAT SATISFY THE FOLLOWING CONDITION:.
1. EIGENVALUES OF HERMITIAN OPERATORS ARE REAL.
2. EIGENFUNCTIONS OF HERMITIAN OPERATORS ARE ORTHOGONAL.
2 To every observable/dynamical variable in Classical Mechanics there is a linear, Hermitian
operator in Quantum Mechanics.
COMMUTATORS
IN GENERAL, THE ORDER OF OPERATIONS MATTERS WHEN DEALING
WITH QUANTUM OPERATORS.
WHEN A COMMUTATOR VALUES TO ZERO, WE SAY THAT THE
OPERATORS “COMMUTE”, THAT IS, THEY CAN BE SIMULTANEOUSLY
DETERMINES WITH ANY DEGREE OF ACCURACY.
FOR CONJUGATE PAIRS WHERE THE UNCERTAINTY PRINCIPLE
RESTRICTS LIMIT OF ACCURACY OF SIMULTANEOUS MEASUREMENTS,
THE OPERATORS DO NOT COMMUTE.
2 To every observable/dynamical variable in Classical Mechanics there is a linear, Hermitian
operator in Quantum Mechanics.
COMMUTATORS
FOR EXAMPLE, ACCORDING TO UNCERTAINTY PRINCIPLE, VARIABLES
OF POSITION AND MOMENTUM ALONG THE SAME DIRECTION CANNOT
BE SIMULTANEOUSLY KNOWN. THEREFORE-
QUESTION
TIME
EVALUATE THE COMMUTATOR:
QUESTION
ASSUME M IS THE MASS OF THE PARTICLE AND PX IS THE
LINEAR MOMENTUM OPERATOR ALONG X DIRECTION.
ANSWER
3 In any measurement of the observable associated with an operator ˆ A, the only values that
will be observed are the eigenvalues a, which satisfy the Eigenvalue equation.
EIGENVALUE EQUATIONS: AN OPERATOR ACTING ON AN OPERAND AND YIELDS THE
OPERAND WITH A MULTIPLICATION CONSTANT.
The Time-Independent Schroedinger Equation is an example
of an Eigenvalue Equation.
4 If a system is in a state described by normalized wave function , then average
(“expectation value”) of an observable is given by the formula-
NOTE: The above equation is considering the above equation is normalized. When not
normalized, the equation goes as follows:
5 The time-evolution of wave function is governed by time-dependent Schrödinger
equation (TDSE)-
BUT, BEFORE THAT...
THE SCHROEDINGER EQUATION
The total energy, W of a single particle in classical mechanics is given as:
NOW, the quantum mechanical equivalent for this is:
Inserting Ψ(x,y,z,t) into this, we get the TIME DEPENDENT SE (TDSE)
THE SCHROEDINGER EQUATION
Ψ(x,t) can be written as Ψ(x) multiplied by a time dependent variable, like f(t):
Now, if we divide both sides of the TDSE by Ψ(x,y,z)f(t), we get:
One of the solutions gotten is Time Independent Schroedinger Equation (TISE):
The solutions of the
TISE are called
Stationary States
QUESTION
TIME
ANSWER
6 Ψ(x,y,z) must be a “WELL-BEHAVED” function:
Ψ IS FINITE, CONTINUOUS AND SINGLE-VALUED FOR ALL VALUES OF X, Y, Z IN THE ENTIRE
CONFIGURATION SPACE.
IF Ψ WERE INFINITE AT ANY POINT, IT WOULD MEAN THAT THE PROBABILITY DENSITY
WOULD ALSO BE INFINITE HENCE, THE Ψ WOULD BE NON-NORMALIZABLE.
ALSO, Ψ MUST BE SINGLE VALUED, OTHERWISE IT WILL CORRESPOND
TO DIFFERENT PROBABILITY DENSITY AT A PARTICULAR POSITION, WHICH IS NOT
POSSIBLE.
Ψ MUST BE SQUARE INTEGRABLE TO ALLOW FOR BORN INTERPRETATION.
dΨ/dx, dΨ/dy, dΨ/dz IS FINITE, CONTINUOUS AND SINGLE-VALUED FOR ALL VALUES OF X,
Y, Z IN THE ENTIRE CONFIGURATION SPACE.
QUESTION
TIME
Assume that the wave function of a particle in 1D
box is given as ψ(x) =Ax(L − x), for 0 ≤ x ≤ L and zero
QUESTION
otherwise. Check whether the wave
function is acceptable or not. If yes, find the
normalization constant A.
ANSWER
QUANTUM
MECHANICAL
MODEL OF
SIMPLE SYSTEMS
GENERAL IDEA
QUANTUM SYSTEMS
Algorithm
The general idea when solving quantum systems is:
Use Schrodinger’s equation
Apply boundary conditions
Resubstitute and Analyze!
THINGS TO The general solution to
NOTE the equation is:
This will be used to obtain
sinusoid solutions to TISE
FREE PARTICLE “Free” particle means a particle moving in a
straight line without the influence of any
potentials (V(x) = 0)
General solution for this goes like:
And Energy is: (for free particle, energy is NOT
QUANTIZED and k can take any values)
PARTICLE IN 1D BOX
1. SINCE for 0<x<a, V(x)=0, TISE for this system is:
2. Boundary Conditions:
Ψ(x)=0 at x=0 and x=a
3. Final Wavefunction of the system:
PARTICLE IN 1D BOX
4. To find the constant A, we need to apply
NORMALISATION CONDITION (refer page 8):
This ultimately gives:
5. Finally to find a relation for the ENERGY OF THE
This ultimately gives: SYSTEM, substitute the wavefunction in the eq.:
PARTICLE IN 3D BOX
We write ψ(x, y, z) = φx(x)φy (y)φz (z) and then divide
throughout by φx(x)φy (y)φz (z)
Mathematically, the above equation is only
possible when the energy can also be separated
into three different components::
PARTICLE IN 3D BOX
HENCE, WE GET THE FOLLOWING WAVEFUNCTION:
And the energy of the system can be written as-
DEGENERACY
Two quantum states are said to be degenerate when they
have the same net energy level but are not identical states.
The degeneracy scenario is mostly observed in a multi-
dimensional potential well, like a 2D BOX.
Since the wave of the particle in the X and Y axes are
independent, it is possible that the particle in the X axis has
the n_x = 1 state and the particle in the Y axis has the n_y = 0
state.
Conversely, it is also possible that n_x = 0 and n_y = 1.
Since the energy is given by :
In both the cases the energy is
equal! Thus the states are
degenerate.
QUESTION
TIME
HARMONIC OSCILLATOR
A Harmonic Oscillator is a quantum system which assumes
particles to be a collection of spring masses.
The potential of a particle is taken as the spring potential
energy of extention/compression.
The solution obtained leads us to an energy function
quantized with the frequency. In simple terms, the energy
has discrete values in terms of the frequency of the
particle wave.
All The Best!
WithLove, the AMs!
