Quantum Mechanics
Dr Bipul Bezbaruah
Sunday, March 13, 2022 1
Wave function
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Physical Representation of wave function
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Properties well behaved Wave Functions
The wave function must be finite everywhere.
The wave function must be single valued.
the wave function and its derivative must be continuous.
The wave function should be normalized
In order to normalize the wave functions, they must approach
zero as x approaches infinity.
The wave function should calculate the average value for a given
variable
The wave function allows calculations via Schordinger equation
The probability distribution is distributed in three dimensions
Solutions that do not satisfy these properties do not generally
correspond to physically realizable circumstances.
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Wave function for a particle
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The Schrödinger Wave Equation
The Schrödinger wave equation in its time-dependent form for a
particle of energy E moving in a potential V in one dimension is
The extension into three dimensions is
where is an imaginary number.
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General Solution of the Schrödinger Wave Equation
The general form of the wave function is
which also describes a wave moving in the x direction.
In general the amplitude may also be complex.
The wave function is also not restricted to being real.
Notice that the sine term has an imaginary number. Only
the physically measurable quantities must be real.
These include the probability, momentum and energy.
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Normalization and Probability
The probability P(x) dx of a particle being between x and X + dx
was given in the equation
The probability of the particle being between x1 and x2 is given
by
The wave function must also be normalized so that the
probability of the particle being somewhere on the x axis is 1.
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Time-Independent Schrödinger Wave Equation
The potential in many cases will not depend explicitly on time.
The dependence on time and position can then be separated in the
Schrödinger wave equation. Let ,
which yields:
Now divide by the wave function:
The left side of Equation (6.10) depends only on time, and the right side
depends only on spatial coordinates. Hence each side must be equal to
a constant. The time dependent side is
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We integrate both sides and find:
where C is an integration constant that we may choose to be 0. Therefore
This determines f to be
This is known as the time-independent Schrödinger wave equation, and it is a
fundamental equation in quantum mechanics.
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Stationary State of wave function
The wave function can be written as:
The probability density becomes:
The probability distributions are constant in time. This is a standing
wave phenomena that is called the stationary state.
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Momentum Operator
To find the expectation value of p, we first need to represent p in terms
of x and t. Consider the derivative of the wave function of a free particle
with respect to x:
With k = p / ħ we have
This yields
This suggests we define the momentum operator as .
The expectation value of the momentum is
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Position and Energy Operators
The position x is its own operator as seen above.
The time derivative of the free-particle wave function is
Substituting ω = E / ħ yields
The energy operator is
The expectation value of the energy is
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Particle in a box
As a first approximation to an electron bound to a hydrogen atom,
consider a “particle in a box,” i.e. a particle of mass m confined to a
region between x = 0 and x = L. The potential energy is zero inside the
“box” and infinite outside (see figure at lower right). The equation
inside the box will be the same as for a free particle (U(x) = 0), but if it
has finite total energy, then it cannot exist outside the box. This
changes the solutions due to the boundary conditions.
Particle in a box: Wave functions, energy levels
Because of the boundary conditions (x) = 0 at x = 0 and x = L, only
certain wavelengths are permissible, exactly as we saw for standing
waves in a closed pipe, or on a string with tied ends. The energy levels
and associated stationary-state wave functions (x) for a particle in a
box are shown. To see this, start with our earlier solution to the 1D
time-independent Schrödinger equation:
x A1eikx A2e ikx A1 A2 cos kx i ( A1 A2 ) sin kx
The boundary conditions will require certain constraints on constants
A1 and A2. We have (0) = A1 + A2 = 0 => A2 = –A1 and (L) = 2iA1sin
kL = 0. Writing 2iA1 = C (a constant), the specific solution is (x) =
Csin kL. But the sine function is zero for any k = np/L. Final solution:
(x) = Csin npx/L . What are the energies? p2 2 2
k
E
2m 2m
n 2p 2 2
2mL2
Note, n = 0 is not
a solution (would
imply (x) = 0
everywhere.
Particle in a box: Probability and normalization
Note that this view of matter as waves leads
directly to the idea of quantized energy levels!
The figure at right shows the first three
stationary-state wave functions (x) for a particle
in a box (top) and the associated probability
distribution functions |(x)|2 (bottom). There are
locations where there is zero probability of
finding the particle. What about the constant C
in our solution (x) = Csin npx/L ?
Wave functions must be normalized so that the
integral of the probability density function |(x)|2
over all x equals 1 (which means there is 100%
probability of finding the particle somewhere).
2 np x
dx 1
2 2
( x ) dx C sin
L
We can evaluate this using the identity sin2q = ½
(1 cos 2q ) to get C = (2/L)½. The final,
normalized solution is then
2 np x
n ( x) sin
L L
Quantization
Boundary conditions of the potential dictate that the wave function must
be zero at x = 0 and x = L. This yields valid solutions for integer values
of n such that kL = nπ.
The wave function is now
We normalize the wave function
The normalized wave function becomes
These functions are identical to those obtained for a vibrating string with
fixed ends.
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Quantized Energy
The quantized wave number now becomes
Solving for the energy yields
Note that the energy depends on the integer values of n. Hence the
energy is quantized and nonzero.
The special case of n = 0 is called the ground state energy.
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Degeneracy
Analysis of the Schrödinger wave equation in three dimensions
introduces three quantum numbers that quantize the energy.
A quantum state is degenerate when there is more than one wave
function for a given energy.
Degeneracy results from particular properties of the potential energy
function that describes the system. A perturbation of the potential
energy can remove the degeneracy.
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