STUDENT WRKSHEET OF PHYSICAL CHEMISTRY I: CHEMICAL STRUCTURE & BONDING

IGMA SANJAYA & DIAN NOVITA

INTRODUCTION TO QUANTUM CHEMISTRY
Basic Competence : Understanding the principle of quantum chemistry
Indicator : 1. To explain the importance of using quantum mechanics to the
behaviour of elementary particles.
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!



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






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.





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STUDENT WRKSHEET OF PHYSICAL CHEMISTRY I: CHEMICAL STRUCTURE & BONDING
IGMA SANJAYA & DIAN NOVITA
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 is the
probability that the particle lies in the volume element 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 possible to have a continuum of
STUDENT WRKSHEET OF PHYSICAL CHEMISTRY I: CHEMICAL STRUCTURE & BONDING
IGMA SANJAYA & DIAN NOVITA
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 a
i
, the wavefunction immediately ``collapses'' into the
corresponding eigenstate
i
(in the case that is a
i
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 {a
n
}. 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 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
STUDENT WRKSHEET OF PHYSICAL CHEMISTRY I: CHEMICAL STRUCTURE & BONDING
IGMA SANJAYA & DIAN NOVITA
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.