Lecture # 2

Models of Atom
Rutherford vs
Bohr

Explains the
Atomic Spectra Uncertainty
(Quantum Principle
Leap)

Schrodinger’s philosophy
“New theory is required to explain the
behavior of electrons”
Wave-Particle de-Broglie
Duality matter waves
for light or l = h/p
electrons
 Need a new theory to understand
(dynamics of) electrons and atoms
• Wavelike equation for describing sub-atomic systems

“Where did we get that (equation) from? Nowhere.

It is not possible to derive it from anything you
know.
It came out of the mind of Schrödinger.”
Schrodinger 1925!!! 2
- Richard Feynman
 Schrodinger’s philosophy

Remember!
Schrodinger’s philosophy
 Laws of Quantum Mechanics
The mathematical description of Quantum mechanics is built upon
the concept of an operator

Classical Variable QM Operator

Laws of Quantum Mechanics
The values which come up as result of an experiment are the
eigenvalues of the appropriate operator

In any measurement of observable associated with operator Â, the

only values that will be ever observed are the eigenvalues an, which
satisfy the eigenvalue equation:

Ψn are the eigenfunctions of the system and an are corresponding

eigenvalues

If the system is in state Ψk , a measurement on the system will yield

an eigenvalue ak
 Schrodinger Equation

In classical mechanics Ĥ represents total energy

We can therefore write

Schrodinger equation is an eigenvalue equation

There can be many solutions ψn(x) each corresponding to different

energy En
 Laws of Quantum Mechanics
1. The state of a system is completely specified by a wave- function Ψ(r,t).
Square of “wavefunction” probability density

2. To every observable in classical mechanics, there corresponds a linear

operator in quantum mechanics

3. In measurement of observable associated with operator A, only values that

will be observed are the (real) eigenvalues of A, which satisfy the eigenvalue
eq.

Ψn are the eigenfunctions of the system and an are corresponding

eigenvalues

If the system is in state Ψk , a measurement on the system will yield an

eigenvalue ak
Laws of Quantum Mechanics
Only real eigenvalues will be observed, which will specify a number
corresponding to the classical variable

If Y(x) = Sin(cx)
d
Y(x) = c ×Cos(cx)
dx
d2
Y(x) = -c 2
× Sin(cx) = -c 2
× Y(x)
dx 2

There may be, and typically are, many

If Y(x) = ea x eigenfunctions for the same QM operator!

d
Y(x) = a × ea x
dx
d2
Y(x) = a 2
× e ax
= a 2
× Y(x)
dx 2
 Schrodinger Equation
Time-dependent Schrodinger equation

Schrodinger equation in 3-dimensions

 Schrodinger Equation
Time-dependent Schrodinger equation

( x , y, z,t )   ( x , y, z )   (t )      
 Schrodinger Equation

LHS is a function of co-ordinates and RHS is function of time. If

these two have to be equal then both functions must be equal to
constant, say W
 Schrodinger Equation

Separation of variables

The solution of the differential equation

  iWt
i   W is  (t )  e
t
 Schrodinger Equation

In classical mechanics Ĥ represents total energy

We can therefore write

Schrodinger equation is an eigenvalue equation

There can be many solutions ψn(x) each corresponding to different

energy En
 Laws of Quantum Mechanics
4. All the eigenfunctions of Quantum Mechanical operators are
“Orthogonal”
+¥

ò m (x)yn (x)dx = ym yn = 0 for m ¹ n

y *

-¥
 Laws of Quantum Mechanics
5. The average value of the observable corresponding to operator  is

a    * Aˆ d

From classical correspondence we can define average values for a

distribution function P(x)
 
x   xP( x)  dx and x 2
  x 2 P( x)  dx
 

<a> corresponds to the average value of a classical physical quantity

or observable , and  represents the corresponding Quantum
mechanical operator
 What can you get from solving the Schrodinger
Equation?

 is a mathematical function; real or complex

What is the meaning of ψ(x,t)?

 Born Interpretation

Classical wave equation:

Ψ(x,t) = Amplitude and |Ψ(x,t)|2 = Intensity

Quantum mechanical system:

• The state is completely specified by a wavefunction Ψ(x,t) ,which

can be complex

• All possible information can be derived from Ψ(x,t)

• Intensity is equivalent to Probability.

• |Ψ(x,t)|2 = P(x)
 Born Interpretation

Probability density
2
P ( x )  ( x , t )    ( x , t )  ( x , t )

Probability
2
P ( xa  x  xa  dx )  ( x ,t ) dx    ( xa ,t )  ( x a ,t )dx

Probability in 3-dimensions

P( xa  x  xa  dx, ya  y  ya  dy, za  z  za  dz )
 * ( xa , ya , za , t ').( xa , ya , za , t ')dxdydz
2
 ( xa , ya , za , t ') d
 6. Normalization of Wavefunction

Since Ψ*Ψdτ is the probability, the total probability Ψ

∞ ∞
of finding the particle somewhere in space has to be
unity

  * ( x, y, z ). ( x, y, z )dxdydz

∞
x

all space ∞

 
all space
 *d     1
If function diverges, i.e.  ∞: Ψ can not be
Ψ
normalized, and therefore is NOT an acceptable
x
wave function. However, a constant value C ≠ 1 is
perfectly acceptable. Unacceptable wavefunction

Ψ must vanish at ±∞, or more appropriately at the boundaries and Ψ

must be finite
 Restrictions on wavefunction

ψ must be a solution of the Schrodinger equation

ψ must be normalizable: ψ must be finite and 0 at boundaries/

±∞

Ψ must be a continuous function of x,y,z

dΨ/dq must be must be continuous in q

Ψ must be single-valued

Ψ must be quadratically-intergrable
(square of the wavefunction should be integrable)

Origin of quantization
 Restrictions on wavefunction

Unacceptable because Unacceptable because

ψ is not continuous dψ/dq is not continuous

Unacceptable because Unacceptable because

ψ is not single-valued ψ goes to infinity
 Essence of Quantum Mechanics

• Not deterministic: Can not precisely determine many

parameters in the system, but Ψ can provide all the information
(spatio-temporal) of a system.

• Only average values and probabilities can be obtained for

classical variables, now in new form of “operators”.

• Total energy is conserved, but quantization of energy levels

come spontaneously from restriction on wave function or
boundary condition

• Final outputs tally very well with experimental results, and does
not violate Classical mechanics for large value of mass.
 Quantum Mechanics

Examples of Exactly Solvable Systems

1. Free Particle
2. Particle in a Square-Well Potential
3. Hydrogen Atom

(xe,ye,ze)
Restrictions on wavefunction

ψ must be a solution of the Schrodinger equation

ψ must be normalizable: ψ must be finite and 0 at

boundaries/ ±∞

Ψ must be a continuous function of x,y,z

dΨ/dq must be must be continuous in x,y,z

Ψ must be single-valued

Ψ must be quadratically-intergrable
(square of the wavefunction should be integrable)

Boundary conditions: Quantization