General Chemistry (CHEM F111)
Lecture-3
16/01/2024
(F-103)
Recap
1. Line-spectra of H-atom
2. Electron-diffraction
3. Wave-particle duality
4. Two-slit experiment
5. Heisenberg Uncertainty principle
6. Wavefunction
The frequencies (in wave numbers) at which the
lines occur in the spectrum of hydrogen are given
by the formula
= 1/ = RH(1/n12 − 1/n22)
where RH = 109677 cm-1 is the Rydberg constant, n1
and n2 > n1 are positive integers, the various series
corresponding to Lyman (n1 = 1), Balmer (n1 = 2),
Paschen (n1 = 3), Brackett (n1 = 4), Pfund (n1 = 5).
Wave-Particle Duality
de Broglie: Just as light exhibits both ‘wave-like’
(diffraction), and ‘particle-like’ characteristics, so should
all material objects.
For light (photon) E = pc = hc/
p = h/
de Broglie (1924) suggested that this is more generally true
of all material objects. A particle moving with linear
momentum p, has an associated ‘matter-wave’ of wave
length
= h/p
Two-slit experiment with microscopic particle like
electrons/photons etc.
Arrive in identical lumps – particles, but
distribution shows interference – wave behaviour.
Heisenberg Uncertainty Principle
It is impossible to specify simultaneously, with
arbitrary precision, (a given Cartesian component
of) the momentum and position of a particle.
px x ħ/2
•Complementary variables, increase in the
precision of one possible only at the cost of a loss of
precision in the other.
•Trajectories not defined precisely.
Uncertainty Principle
Definite wavelength Definite momentum but since wave
is spread out everywhere, no information about position.
Superposition of waves of definite wavelength to yield a
localized wavefunction – momentum not precisely defined.
Wavefunction for particle with precisely defined
position
Invalid Assumptions of Classical
Physics
1. Particle travels in a trajectory or path, with a precise
position and momentum at each instant.
2. Any type of motion can be excited to a state of arbitrary
energy.
3. ‘Waves’ and ‘Particles’ are distinct concepts.
These are excellent assumptions at the macroscopic level,
but break down when one considers the behaviour of very
small entities such as electrons, atoms, molecules, etc.
Today’s topic
1. Wavefunction, Born interpretation and
stationary state
2. Schrodinger eqn. (Eqn. for de Broglie
wave)
3. Well-behaved wavefunction for a
physical system
4. Operators, and Eigen value equation
5. Free particle
WAVEFUNCTION / (PSI)
The state of a system (particle) is completely specified by
its wavefunction (x,y,z,t), which is a probability
amplitude and has the significance that
2 dV
(more generally 2dV since may be complex)
represents the probability that the particle is located in the
infinitesimal element of volume dV about the given point,
at time t.
(Born interpretation of wavefunction)
Stationary States
In many situations of interest in chemistry, one is
concerned with stationary states, in which the
probability distribution is independent of time. The
part of which depends on t is simple in such
states, and factors out.
For such states,
ψ2 dV
represents the (time-independent) probability
distribution, where the wavefunction ψ(x,y,z) is a
function of the spatial coordinates alone.
2 is physically significant
Schrodinger Equation
(An equation for de Broglie’s
matter wave)
The wavefunction satisfies the Schrodinger equation
Ĥψ=Eψ
where Ĥ is called the Hamiltonian operator, a set of well
defined operations to be carried out on the function ψ, and
represents the energy. In one dimension, the Hamiltonian
may be written as
Ĥ = (−ħ2/2m) d2/dx2 + V(x)
where V(x) is the potential energy to which the particle is subjected.
Operators
For every observable in classical mechanics, there
is a corresponding operator in quantum mechanics.
Observables in Quantum mechanics: Apply the operator on
the state function of the systems – outcome will be observable.
Operators and eigen value equation
Schrodinger eqn is an eigen value eqn.:
Ĥψ=Eψ
Operator: Ĥ, eigen function: ψ, eigen value: E
Example:
dx
(
d ax
e ) = a(e )
ax
d/dx (operator) acting on eax (eigen function)
giving eigen value = a
Well behaved wavefunction for a physical system
Four conditions are put forward to make probability functions,
which are solution of Schröndinger equations, consistent with
a reasonable picture of nature.
• Ψ must be single-valued.
• Ψ must be finite everywhere.
• Ψ must be continuous.
• 𝑑ψ/𝑑𝑥 must be continuous.
Normalization of wavefunction
is a consequence of Born
Interpretation.
An unacceptable wavefunction because
(a) it is not single-valued,
(b) it is infinite over a finite range,
(c) it is not continuous,
(d) its slope is not continuous.
Schrodinger equation
The Schrodinger equation for a microscopic
particle of mass m moving in one dimension may
thus be written as
−(ħ2/2m) d2ψ(x)/dx2 + V(x)ψ(x) = Eψ(x)
where E is the energy.
In three dimensions,
−(ħ2/2m) (2 ψ/x2 + 2 ψ/y2 + 2ψ/z2) +
V(x,y,z)ψ(x,y,z) = Eψ(x,y,z)
Solutions to the time-independent
Schrodinger equation for some
simple systems
Free particle in one dimension
−(ħ2/2m) d2(x)/dx2 = E(x)
(x) = sin(kx) where k = (2mE)1/2/ħ
whence E = ħ2k2/2m
But for a free particle, E = p2/2m = ħ2k2/2m
or p = ħk
Now, sin(kx) is a wave of wavelength = 2/k.
Putting the two together, we find
= h/p, the de Broglie relation.
