Chapter 2

Chapter 2
Postulates of Quantum Mechanics
Postulate 1. The state of a quantum mechanical system is completely specified by a function ψ(r, t) that
depends on the coordinates of the particle(s), r and on time, t. This function, called the wave function or state
function, has the important property that | | is the probability that the particle lies in the volume
element located at r at time t.
The wavefunction must satisfy certain mathematical conditions because of this probabilistic interpretation. For
the case of a single particle, the probability of finding it somewhere is 1, so that we have the normalization
condition
(1)
It is customary to also normalize many-particle wave functions to 1. The wave function must also be single-
valued, continuous, and finite.
Wave function Properties
1. Contains all the measurable information about the particle.

2. Must be a continuous function of x.
3. Must be normalizable. This implies that the wave function approaches zero as x approaches infinity.
4. Ψ* Ψ summed over all space = 1 (if the particle exists, the probability of finding it somewhere must be
one)
5. Establish the probability in three dimensions
6. Permits calculation of effective average value (expectation value) of a given variable
7. The slope of the function in x must be continuous. Specifically must be continuous.
8. Must be a solution of the Schrodinger equation. Applying the boundary conditions on the solutions, it is
possible todetermine the energy eigenvalues.
Postulate 2. To every observable in classical mechanics there corresponds a linear, Hermitian operator in
quantum mechanics.
If we require that the expectation value of an operator ̂ is real, then ̂ must be a Hermitian operator. Some
common operators occuring in quantum mechanics are collected in Table 1.
Table 1: Physical observables and their corresponding quantum operators (single particle)
Observable Observable Operator Operator
Name Symbol Symbol Operation
Position Multiply by
Momentum
Page 1 of 6
Chapter 2
Kinetic energy
Potential energy
Multiply by
Total energy
Angular momentum
Postulate 3. In any measurement of the observable associated with operator ̂ , the only values that will ever be
observed are the eigenvalues a, which satisfy the eigenvalue equation
̂ (2)
This postulate captures the central point of quantum mechanics--the values of dynamical variables can be
quantized (although it is still possible to have a continuum of eigenvalues in the case of unbound states). If the
system is in an eigenstate of ̂ with eigenvalue, then any measurement of the quantity A will yield a.
Postulate 4. If a system is in a state described by a normalized wave function , then the average value of the
observable corresponding to ̂ is given by
(3)
Postulate 5. The wave function or state function of a system evolves in time according to the time-dependent
Schrödinger equation
(4)
Postulate 6. The total wavefunction must be antisymmetric with respect to the interchange of all coordinates of
one fermion with those of another. Electronic spin must be included in this set of coordinates.
The Pauli exclusion principle is a direct result of this antisymmetry principle. We will later see that Slater determinants
provide a convenient means of enforcing this property on electronic wavefunctions.
Operators
Operator is a rule that transforms a given function into another function. The differentation operator is an example--it
transforms a differentiable function f(x) into another function f’(x). Other examples include integration, the square root,
and so forth. Numbers can also be considered as operators (they multiply a function). McQuarrie gives an even more
general definition for an operator: ``An operator is a symbol that tells us to do something with whatever follows the
symbol''.
In quantum mechanics, physical observables (e.g., energy, momentum, position, etc.) are represented (
Page 2 of 6
Chapter 2
mathematically by operators. For instance, the operator corresponding to energy is the Hamiltonian operator 5
)
where is an index over all the particles of the system. We have already encountered the single-particle
Hamiltonian in equation. The average value of an observable A represented by an operator ̂ for a quantum
molecular state is given by the ``expectation value'' formula
(6)
Hilbert Space
Hilbert space H is a real or complex inner product space that is also a complete metric space with respect to the
distance function induced by the inner product.
To say that H is a complex inner product space means that H is a complex vector space on which there is an
inner product (x, y) associating a complex number to each pair of elements x, y of H that satisfies the following
properties:
1. The inner product is conjugate symmetric; that is, the inner product of a pair of elements is equal to
the complex conjugate of the inner product of the swapped elements:
(Ψ,Φ) = (Φ,Ψ)*
2. The inner product is linear in its first argument. For all complex numbers a and b,
(aΨ1+ bΨ2, Φ) = a(Ψ1, Φ) + b(Ψ2, Φ)
3. The inner product of an element with itself is positive definite:
It follows from properties 1 and 2 that a complex inner product is conjugate linear in its second argument, meaning
that
A real inner product space is defined in the same way, except that H is a real vector space and the inner product
takes real values. Such an inner product will be bilinear: that is, linear in each argument.
The norm is the real-valued function
‖ ‖ √
and the distance d between two points x, y in H is defined in terms of the norm by
‖ ‖ √
Page 3 of 6
Chapter 2
Linear Vector Space
Page 4 of 6
Chapter 2
Page 5 of 6
Chapter 2
Page 6 of 6

Chapter 2

Uploaded by

Copyright:

Available Formats

Chapter 2

Uploaded by

Document Information

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Chapter 2

Uploaded by

Copyright:

Available Formats

Chapter 2

Postulates of Quantum Mechanics

1. Contains all the measurable information about the particle.

Linear Vector Space

You might also like