The Postulates of Quantum Mechanics

• Some of the basic postulates of quantum mechanics will now be introduced.

• The postulates are the fundamental assumptions on which quantum mechanics is based.
• For example, Newton’s three laws are postulates of classical mechanics.
• These postulates cannot be derived!
• Newton’s Laws, are postulates and are believed to be correct for macroscopic systems base on
agreement with experiment.
• The postulates of Quantum Mechanics also cannot be derived.
• They too are believed to be correct for both microscopic and macroscopic worlds based on agreement
with experiment.
• The postulates of quantum mechanics can be expressed in many ways:
• People present them in different order and the number of postulates is often different (some are combined).
• The postulates are connected as a whole.
• They may be very strange at first.
• Applications will help us understand. 1
 Postulate 1
• The first postulate states that the wave function of a quantum mechanical system contains all
information concerning the system.
• The state of a quantum mechanical system is completely specified by a function Y(x, y, z ,t) that
depends on the coordinates and on time.
• This function is called the wave function of the system.
• All possible in formation about the system can be derived from Y.
• Example of a Wave function:
• The wave function for a one-dimensional harmonic oscillator is:

Where; a and C are constants and the variable x is the displacement of the diatomic from equilibrium.
• Notice the wave function can be complex (and complicated)!
• More on the properties of the wave functions later.
• For this idealized system, we can derive any property of the system from the above function. 2
 Postulate 1 (extended)
• The state of a quantum mechanical system is completely specified by a function Y(x, y, z, t) that
depends on the coordinates and on the time.
• This function is called the wave function of the system. All possible information about the system
can be derived from Y.
• The wave function Y(x, y, z, t) has an important property that its square is the probability
distribution function for the system:

• Complex conjugate of the wave function is obtained by replacing any imaginary numbers with their
negative: i* = -1.

Example:

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 Minimal Requirements for a Valid Wave Function

• In general (x, y, z, t) must satisfy the following conditions:

1. Ψ (x, y, z, t) must be a continuous function.

• There cannot be points in space where the wave function is “missing”. There must be a
probability associated with every point in space.

2. Ψ(x, y, z, t ) must be single-valued and bounded.

• At a given x, y, z and t, Ψ can only have one value.
• The value of the wave function cannot be infinite anywhere.
• There cannot be two or more probabilities of finding the particle at a single point in space.
• There cannot be an infinite probability of finding the particle at a single point in space.
• The probability can at most be 1 which corresponds to 100%.
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Examples
Normalize the following functions, if possible, for the intervals given.

4. ψ (x, y, z, t) should have partial derivatives:

that are continuous functions of x, y, z.
• This is a looser requirement for a ‘good’ wave function.
• There are sometimes cases when this is relaxed.
• For example, when potential is ill-behaved. (e.g. Coulomb potential at the nucleus is infinite)

 Conditions 1 through 4 are the requirements for a ‘well-behaved’ function. 6

 Postulate 2
• The second postulate states that for every physical observable, there corresponds a quantum
mechanical operator!
• To every “observable” in classical mechanics there corresponds an operator in quantum
mechanics.
What is an operator?
• An operator is a mathematical entity or symbol that tells you to do something to whatever
follows the symbol.

• Operators usually denoted with a carat ^ over it, e.g. 𝑂෠

• In these lecture notes will sometimes use (in the text) a bold underscore, e.g. O
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• To every observable in classical mechanics there corresponds an operator in quantum
mechanics.
• To find the operator, write down the classical-mechanical expression for the observable in
terms of Cartesian coordinates and linear momentum, and make the following replacements:

• Where; is the reduced Planck’s constant and is pronounced ‘h-bar’.

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 Postulate 3
• The 3rd postulate deals with measurements in quantum mechanics.
• Any measurement of the observable associated with the operator A, the only values that will
ever be observed are the eigenvalues ‘a’, which satisfy the following:
Where; f is an eigenfunction of the operator A (It is not necessarily the wave function).
What are Eigen functions and Eigenvalues?
• When a mathematical operation (such as multiplication, differentiation) is performed on a function,
the result is generally some different function.
• For example: differentiation of x2 yields a different function, 2x.
• For some combinations of operations and functions, the same function is regenerated, multiplied by a
constant.
• For example: differentiation of e2x yields a different function, 2e2x.
• The original function is simply multiplied by 2. 9
 ෡ (if so, what is the eigen value?)
• Determine if the function f is an eigenfunction of the operator 𝑨

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 Postulate 3
෡ , the only values that
• For any measurement of the observable associated with the operator 𝑨
will ever be observed are the eigenvalues an which satisfy:

• An operator generally has more than one valid eigenfunction so we index the eigen functions
with a subscript n.
• The eigen value ‘a’ can be discrete or continuous, depending on the operator.
• If the eigenvalues are discrete then we usually index them from the smallest value to the
largest value: n = (sometimes) 0,1, 2, 3….

• If the eigenvalues are continuous, we usually drop the subscript.

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 Postulate 4
• If a system is in a state described by a normalized wave function Y, then the average or mean value
of the observable that will be measured corresponding to the operator A is given by:

• The above is called the expectation value in quantum mechanics.

• If we have a wave function and an operator corresponding to an observable we want to measure, the
above tells us what the average value we will measure at a given time.
• Let’s write this out more explicitly:

• Brackets are used to emphasize that we apply the operator to Y before we integrate.
• If the wave function Y is not normalized, then the expectation value is
given by:

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 Postulate 5
• If the potential does not change in time, the wave function can be obtained by solving for Schrödinger’s time-
independent equation.

• Where H is the Hamiltonian operator given by:

• We can use the Schrödinger equation to solve for the wave function for any system. (in principle).
• The potential energy function V cannot be given in general because it depends on the system.
• In this course, the systems we are interested in usually have a potential which does not depend on time.

• In this case, we can simplify things.

• The wave function of a system evolves in time according to the time-dependent Schrödinger
equation:

• With the total wave function given by:

• Thus, we don’t have to solve the time-dependent wave equation, only the time-independent
equation, because the time-dependent component of the total wave function is always the same.
• We will use Schrödinger’s time independent equation extensively in this course. 13