STUDENT WRKSHEET OF PHYSICAL CHEMISTRY I: CHEMICAL STRUCTURE & BONDING

INTRODUCTION TO QUANTUM CHEMISTRY

Basic Competence : Understanding the principle of quantum chemistry
Indicator

: 1. To explain the importance of using quantum

mechanics
particles.

to

the

behaviour

of

elementary

2. To distinguish the time-dependent with time

independent Schrodinger equation

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WORKSHEET 002
1. Write down the Schrodinger equation as the basis of quantum
chemistry!

E
H

2. We know the time-dependent Schrodinger equation and the timeindependent Schrodinger equation.
a. Write down the two forms of the Schrodinger equation!
The
time-dependent
Schrodinger equation

The time-independent
equation

Schrodinger

b. Explain the differences in the use of the time-dependent

Schrodinger equation and the time-independent Schrodinger
equation!
The time independent Schrodinger equation for a particle of mass m
moving in one dimension with energy E in a system that does not
change with time (for instance its volume remains constant). The factor
U(x) is the potential energy of the particle at the point x, because the
total energy E is the sum of potential and kinetic energy of the particle.
The potential energy term does not depend on time. But on The time
dependent Schrodinger equation, The potential energy depends on
space and time.

IGMA SANJAYA & DIAN NOVITA

STUDENT WRKSHEET OF PHYSICAL CHEMISTRY I: CHEMICAL STRUCTURE & BONDING

3. Write the postulates of quantum mechanics and make a summary

of the consequences of its use!
Postulate I
The state of a quantum mechanical system is completely specified
by a function
that depends on the coordinates of the particle(s) and
on time. This function, called the wave function or state function, has the
important property that
lies in the volume element

is the probability that the particle

located at

at time

Summary of the consequences:

Since the probability of a particle being somewhere in space is
unity, the integration of the wavefunction over all space leads to a
probability of 1. That is, the wavefunction is normalized:

In order for Y (x,t) to represent a viable physical state, certain

conditions are required:
1. The wavefunction must be a single-valued function of the spatial
coordinates. (single probability for being in a given spatial interval)
2. The first derivative exists in order to satisfy the Schrodinger equation.
3. The wavefunction cannot have an infinite amplitude over a finite
interval. This would preclude normalization over the interval.
Postulate II
To every observable in classical mechanics there corresponds a
linear operator, Hermitian operator in quantum mechanics.
Summary of the consequences:
This postulate comes about because of the considerations raised in
hermitian operator. 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.
Quantum mechanical operators are classified as Hermitian
operators as they are analogs of Hermitian matrices, that are defined as
having only real eigenvalues. Also, the eigenfunctions of Hermitian
operators are orthogonal.
Postulate III
In any measurement of the observable associated with operator ,
the only values that will ever be observed are the eigenvalues , which
satisfy the eigenvalue equation
Summary of the consequences:
This postulate captures the central point of quantum mechanics.
The values of dynamical variables can be quantized (although it is still

IGMA SANJAYA & DIAN NOVITA

STUDENT WRKSHEET OF PHYSICAL CHEMISTRY I: CHEMICAL STRUCTURE & BONDING

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 will yield .

Although measurements must always yield an eigenvalue, the state
does not have to be an eigenstate of initially. An arbitrary state can be
expanded in the complete set of eigenvectors of

as

An important second half of the third postulate is that, after

measurement of

yields some eigenvalues ai, the wavefunction

immediately ``collapses'' into the corresponding eigenstate

(in the

case that is ai degenerate, then

becomes the projection of
onto the
degenerate subspace). Thus, measurement affects the state of the
system. This fact is used in many elaborate experimental tests of quantum
mechanics.
The total wavefunction defining a given state of a particle need not
be an eigenfunction of the operator (but no one can expand the
wavefunction in terms of the eigenfunctions of the operator as a complete
basis).
Postulate IV
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

Summary of the consequences:

Postulate 4 tells us how to calculate the average in a series of
measurements. If
(x) is an eigenstate of , then we observe only one
value of a, but in the general case, when we carry out a series of
measurements, we observe a distribution of the set of possible results
{an}. If the system is in a state described
(x), the probability of
obtaining the particular result an in a single measurements, we consider a
measurement of the energy, so that =H and (a)=(E).
Postulate V
The wavefunction or state function of a system evolves in time
according to the time-dependent Schrdinger equation

Summary of the consequences:

The Hamiltonian operator H contains the kinetic and potential
operators. This equation reflects the deterministic (newtonian) nature of
particles/waves. It appears to be in contrast to Postulate 4 (many

IGMA SANJAYA & DIAN NOVITA

STUDENT WRKSHEET OF PHYSICAL CHEMISTRY I: CHEMICAL STRUCTURE & BONDING

observations lead to different measured observables, each weighted

differently, i.e., a probabilistic view of the particle/wave). The
reconciliation is in the fact that Postulate 4 certains to the outcomes of
measurements at a specific instant in time. Postulate 5 allows us to
propagate the wavefunction in time. Then, at some future time, if we
make another measurement, we are again faced with the implications of
Postulate 4.

IGMA SANJAYA & DIAN NOVITA