TITLE

Inadequacy of Classical Mechanics-I

COURSE NAME

Atomic Structure and Chemical Bonding

PAPER

Chemistry -DSC 2A : Atomic Structure, Bonding, General

Organic Chemistry & Aliphatic Hydrocarbons
Section A: INORGANIC CHEMISTRY-I

COURSE (as per CBCS):

 1st Semester: BSc. Chemistry
BSc. Physical Science
(Physics, Chemistry, Mathematics)

 Generic Elective: BSc. Hons. (Chemistry)

Introduction

Hello friends, welcome to the introductory course on “Atomic Structure

and Chemical Bonding”. This course is first of the two 2 credit courses
related to the Core Paper-1 in Chemistry entitled, “Atomic Structure,
Bonding, General Organic Chemistry & Aliphatic Hydrocarbons”. As the
name suggests in this course we will take up two topics i.e. Atomic
structure & Chemical bonding, rest of the topics will be taken up in the
course titled “Organic Chemistry-1, which will be offered separately.

I am Dr. Sanjiv Kumar, Associate Professor in Physical Chemistry at

School of Sciences, IGNOU. I will be your instructor for the course on
‘’Atomic Structure and Chemical Bonding” for next five weeks.

We would spend first two weeks on understanding the Structure of

Atom and over the next three weeks we would learn about Chemical
Bonding. In this course, we would follow “Conceptual development
approach” as against the typical descriptive approach.

As the current understanding of the structure of atom is based on

quantum mechanical approach about which you have had a very brief
exposure in your +2 chemistry course. We would go a little deeper into
the same. Instead of stating the concepts that led to the quantum
mechanical ideas we would gradually build up their understanding and
put them in perspective.

Accordingly our strategy to understand the structure of atom would be

to discuss

o Why of quantum mechanics?

o What is quantum mechanics?

 o How does wave mechanics (one of the approaches of quantum
mechanics) work /operate?

o Quantum / wave mechanical treatment of H-atom

We would spend two sessions on establishing the inadequacy of

classical mechanics and the need for a new theory. We would then
bring in the concept of quantisation and discuss its success. Thereafter
we would briefly discuss the Schrodinger’s wave mechanical formalism
and show is applications. In the process we would learn about the
quantum mechanical description of atomic structure. In the context of
Chemical Bonding we would begin by giving a historical perspective of
the development of the ideas of bonding between atoms. We would
then explain the classical theories of chemical bonding and outline their
limitations.

In the last week, towards the end of the course we would take up ionic
solids in terms of bonding, their structure and energetics of their
formation. We would also take up the weak interactions between the
molecules and molecules and ions before concluding with the
energetics of dissolution.

Let us begin the discussion on atomic structure by the first lecture

attempting to establish the inadequacy of classical mechanics in dealing
with microscopic systems. The lecture plan for today session happens
to be as follows i.e. first we look at what is the basic premise of classical
mechanics i.e. what is classical mechanics, what does it do and how
does it serve our purpose? Thereafter we will see what kind of
experiments are there which pose challenge to classical mechanics i.e.
certain experiments which could not be answered and could not be
explained on the basis of classical mechanics. We will try to have a look
at them and in then this process, I will take up two such important
experiments that happened to be blackbody radiation and
photoelectric effect in today’s session. I will try to see what were the
experiments, what kind of results were obtained and what were the
classical predictions for those experiments and how the two were
mismatching. So in this process we will try to see that our classical
mechanics is inadequate to explain these results. Towards the end we
will try to sum up what we learn in today’s session.

What is Classical Mechanics?

Let’s make a beginning by looking at what is classical mechanics?
Actually if you really ask me classical mechanics is a set of laws that
have been formulated on the basis of our observation of nature over a
period of centuries altogether that means whatever we gathered in
terms of looking at the motion of astronomical bodies, sun, moon and
things all around us. So we see things in a macroscopic world and all
those observations have been documented or formulated in terms of
certain laws and the three basic pillars of classical mechanics are the
newton’s laws of motion, the gravitational law and Maxwell equation.
These three put together, put classical mechanics on a very strong
foundation and on the basis of these, practically most of the things we
know of in the macroscopic world could be explained. Now if that be
so, let’s take some example now.

Let’s see how do we put classical mechanics to use. I am sure that

these pictures will be quite illustrative to you. The first picture here
talks about a baseball game. Same thing happens in the case of even
cricket as well. So if we see here is the player has shot the ball and the
fielder here is trying to assess or ascertain where the ball is going to fall
so that he can anticipate the catch and take it. Same thing happens in
the cricket as well. Now this case we are not making any calculation
per say but we are doing some kind of mental calculation. We see o.k.
where is it, how is it going, how high is it going, where is going to fall?
So anticipate and position ourselves to make a catch. So there is a kind
of mental calculation but all that again based on our understanding of
classical mechanics. O.k. this is one aspect of it. Now here what we see
this is a typical picture and show that most of you would have come
across this picture. This is which I am trying to predict, suppose the ball
had hit because now we know the instrumentation is available now.
The movement the ball leaves the bowler we can work out at what
stage it has gone, what is the force on that, where is going to fall,
where is going to land up eventually thereafter. Whether is going to hit
the stumps or not? That can be predicted fairly well and then we
believe in the outcome of such kind of predictions and even the same
thing happened in case of tennis as well. So there are three instances
from sports that we can put classical mechanics to use and then we
have reasonably good faith on the outcome of such predictions. We
can take certain more examples.

We know that the rocket science, when the launch rocket or a satellite
going out. We know precisely when to plan, all the events which are
going to take place in the process of launch of satellite to it’s the
establishment in the orbit everything is well planned precisely in terms
of time what is going to happen at what height, at what time and so on
so forth. O.k. this all is possible because we know our classical
mechanics laws are perfectly predictable, perfectly useful. Similarly we
can even predict the cosmic events like one you are going to have a
meteor shower, it can be predicted and we actually see it, we can go
roof top and then actually enjoy that thing because it happens the way
it is predicted because we know how it is going to happen in time. Now
that is as regards our validity so to say of classical mechanics.

Towards the end of nineteenth century that is around 1880-90’s people

thought, people in physics particularly thought, that there is nothing
left in physics because they were so contented with the success of
classical mechanics that practical anything which you come across
could be explained fairly well. The only thing probably physicists were
doing at that point of time was to see that if I can make measurement
slightly more accurate. For example, if I have a table, if I measure its
length say it is about 1.7 meters. May be I can use its different scale I
can measure it to say 1.73 meters or may be 1.732 meters or may be I
can go in further down. That means I am just looking forward to extra
decimal place.

So there is nothing new to happen, the only thing is that I am trying to

get more and more accurate measurement and that’s not very
significant. So people thought that nothing is left in physics to the
extent even that physicist by the name Phillip Von Jolly actually advised
Max Planck not to pursue physics but there is nothing what he could
expect from physics to happen at that point of time and fortunately for
us that Max Planck does not listen to him because it’s who it is Max
Planck who actually gave us the quantization concept and quantum
mechanics as we know of today. O.k. now in the backdrop of such a
scenario that everything is predictable.
There were certain experiments, the experimental findings were such
which post challenge to this established kind of branch of science,
domain of science i.e. classical mechanics and the five significant
challenges are the blackbody radiation, photoelectric effect, anomalous
heat capacity of solids, atomic line spectra and compton scattering. In
fact the last one, the fifth one, actually was not a challenge per say but I
am putting it and clubbing it here because this also could not be
explained on the basis of classical mechanics. In fact Compton
scattering was used to kind of verify the photon concept given by
Einstein, we will come to that later on may be in the next session we
will talk about it. And out of this five experiments listed here. In
today’s session I will try to discuss about the first two of them in little
more details we will see what are the experiments, what are these
systems, what kind of results are obtained and then where does
classical mechanics falter in explaining them?

Black Body Radiation

Let’s make a beginning with the first experiment i.e. blackbody
radiation. To come to the blackbody radiation lets understand that we
know that anything which is hot emits radiations and I am sure that you
have experienced while sitting close to a fire place that heat comes to
you in the form of radiation and also you would have seen if you visited
a blacksmith you would have seen that as the blacksmith goes on
heating the iron rod to higher and higher temperature the colour of
iron rod changes. It is a general phenomenon that anything which is
hot is going to emit radiation and the nature of radiation which comes
from hot object will depend on two things: (1) the temperature and (2)
the nature of the material being talked about.

Now this is just a small listing over here. What we see is that when the
temperature is low say around room temperature or so, or my body
temperature for that matter. We all emit what is called as IR radiation
and as the temperature goes up we see that the colour becomes cherry
red if it becomes 1000°C, it becomes yellowish. At higher temperature
becomes white and even beyond 2000°C may be we can expect UV
radiation coming from the hot object. What you see is the output from
a hot object depends on the temperature and I am sure that you would
have come across this ear thermometer now a days is being used
especially for children. The basic principle of this thermometer is that
when you insert the probe into the ear of the child because the body of
the child is emitting the child has fever the temperature is more than
the normal one. So the IR radiations which come that will be sensed by
the sensor of the thermometer and that will display it as a reading on
the thermometer that is a purely very very convenient proposition and
this device has been created by NASA for different purposes is there.
But it’s put to common use now a days.

Now let’s come to what is blackbody? Blackbody actually is an ideal

system and I am sure that we all know that nothing ideal exists per say,
ideal are systems which do not exist on their own but we can come to a
close approximation to them and a blackbody by definition is a body
which absorbs all radiations which fall on it and in turn when heated
emit of radiation out of it. Let’s take an approximation of that. Now
suppose I have a hollow sphere, say I have a sphere which is empty
from inside hollow and I make a small pin hole in that. When I have
that any radiations say this is just depiction of that. Suppose some
radiations gets into this pin hole. So once this gets in, the radiation will
go strike a wall opposite to it and get reflected inside and then this
radiation which is gone into the sphere will get reflected repeatedly
and eventually if it is get absorbed there. No matter what is a kind of
radiation we are throwing on that, that will get absorbed. So in
principle what we can say is such a body is a perfect absorber, it
absorbs all radiations falling on that and if I heat it in turn when the
radiation is come out from such a body that will be giving all possible
radiations. So such a body which is a perfect absorber as well as
perfect emitter is called as a blackbody. So the radiation which comes
from such a body is called as blackbody radiation.

Let’s try to see what are the results we have obtained in case of
blackbody radiation. The three very crucial results what you obtained.
The first one is that as the temperature of blackbody increases what
you find is that the amount of radiation coming off increases i.e. this
gives you some measure of the intensity or energy density because this
axis is energy density that means the amount of energy coming out as
per unit wavelength, so this axis are wavelength and this axis is energy
emitted or energy density energy emitted per unit wavelength. O.k. so
what you find is that as the temperature increases we find that say
from 3500° kelvin to 4000-4500 so on and so forth. As temperature is
being increased we find the energy output is more and more. That
means you can see in terms of area under these curves, the area under
these curves increases that is the first observation. The second
observation here is as the temperature increases we find, say at a given
temperature 3500 K what you find is that this is a kind of distribution
we have at this particular wavelength, there is a maximum energy
coming off. As we increase temperature we find this maxima shifts to
these sides, what we see is the trend of this kind that as temperature
increasing our maxima shift to a lower wavelength. That is something
what you have observed in case of blacksmith example i.e. when the
iron bar is heated more and more the colour changes i.e. the outcome
that is the maximum wavelength is coming out is different over there.
And the third most crucial observation here is that the spectrum
depends on temperature and not on the nature of object i.e. what is
the blackbody made up off, doesn’t matter. The only thing is the
outcome will depend on the temperature of the blackbody. So this is in
contrast to what we had in case of a general observation i.e. the energy
output will depend on the nature as well as the temperature of the
body. So that’s a basic difference over here.

Now classically speaking, there are certain observations we have to see

how do we reconcile with what we experimentally observe. There are
three important things here again. First is your Stefan’s law. Stefan’s
law proposed initially by Stefen’s and later modified by Boltzman; also
called as Boltzman-Stefen’s law what it says is that the rate of emission
of radiation, the radiation energy from surface of a hot object is
proportional to the fourth power of the temperature- its absolute
temperature. what happen is we have the output coming here is
proportionate to T(with power of 4) and that actually experience our
first observation in a way that accounts for the first observation that as
temperature increases the energy output is increasing. Second
important law is what’s called as Wien’s Displacement Law what it says
is the λmax of the wavelength distribution shifts to lower wavelengths
as temperature increases. What it says is that λmax x T is constant, that
means if T goes up, λmax has to come down and this explains shift in
the wavelength of maximum emission. So the two observations are
explained here broadly, that means qualitatively speaking. We said
there will be increase and we find that the increase is there. There will
be shift in λmax that also will be explaining. However when Wien tried
to explain the energy distribution curve, the whole curve as such, in
terms of using Stefen’s Boltzman Law and modifying their further; he
gave an expression which shows that Eλ i.e. Energy emitted at the given
wavelength is inversely proportional to λ(with power of 5) so and so
forth. This agrees to a good extent with the experimental observation.
What you find in this figure is that these dots are our experimental
points and this dotted line here gives you the prediction from Wien’s
law and we find that for lower wavelength Wien’s expression matches
with experiment whereas for high wavelength there is a discrepancy.

Next serious effect was made by Lord Rayleigh and later on modified
slightly by Jeans. What Lord Rayleigh’s said was that the blackbody; he
assumed, the blackbody to be a collection of oscillators. It means that
atoms and molecules constituting the object, the blackbody are
visualized as oscillator over there. That can absorb EM radiation of all
possible frequencies i.e. we talk about the classical mechanics i.e., the
energy is continuous and the second assumption was total energy
which is available to a system is distributed amongst all possible
oscillator in the system. So on the basis of these two assumptions he
really proposed; formulated the following expression and this
expression was in reasonable agreement vis-a-vis the high wavelength
region of the spectrum what we got in case of blackbody radiation. We
find that for the higher wavelength region here, there is an agreement
between experiment and theory. This is your curve from Lord
Rayleigh’s prediction and these are experimental curves. But whereas
for the lower wave region, there is a mismatch over there.

So we find that wien’s law explains the lower wavelength region, Lord
Rayleigh’s proposition explains the high wavelength region but none of
the two gives you the whole curve. That means our classical attempts
to explain black body radiation happen to be inadequate. So we find
that predictions of classical mechanics are not in agreement with
experiments and we find that classical mechanics is inadequate to
explain our blackbody radiation and we need something different from
this mechanics now and such an explanation of the phenomenon was
given by Max Planck in year 1900 about which we will talk may be in
the third lecture.

Photoelectric Effect
Now let’s move on to the second experiment I mentioned earlier which
I want to take up for today i.e. the photoelectric effect. Another very
important experiment which posed a serious challenge to classical
mechanics, the experiment is as follows. Suppose I take certain metal,
a soft metal like cesium or so and if I throw some light on that what we
observe is that when light fallen that it mixed electron from this metal
and if it go on throwing light, electron keeps coming of the mirror and
the electrons which are coming out constitute current. So such an
effect where is getting a electric current as a consequence of light is
called as photoelectric effect and electrons which are emitted because
of light are called as photoelectrons. O.k. so that is a kind of
phenomenon I am talking about. But it’s important is that when this
experiment was studied somewhere around 1887 what we found was
that there are few important observations.

The first observation significant one was i.e. the movement you throw
light we find a current coming over there. The movement switch off
the light, there is no current. That means this emission of electrons
from the metal is instantaneous, there is no time lag between the light
falling on the metal and electrons coming from there, that’s the first
and significant observation. Second observation was that if I throw
light on certain wavelength say certain low frequency, we find that
there is no electron coming out. I increase the frequency slightly we
find that still there is no current coming increase the frequency further
we find o.k. now the current start coming that means electrons need
certain minimum amount of frequency of the radiation for electrons to
be emitted from there. If I go on increasing the frequency, you find
electron keep coming let me the current keeps flowing that electrons
which come there off higher kinetic energy. We need something called
as stopping potential which physicist talk about that means that is how
experiment was designed, that means we try to increase potential so
that we don’t let the electrons to come off, that is called as stopping
potential. Stopping potential actually is a measure of the kinetic energy
of electrons coming off. For us it suffices to know that we need a
minimum amount of frequency of the radiation for the electron to be
coming out from the metal, that is called as a threshold frequency, that
is the second observation.

The third observation was as I just mentioned that if I keep on

increasing frequency. O.k. let’s see that this is a kinetic energy of
electrons, we will try to increase frequency over there. So what you
see is as the frequency is very low, we can see there is no current
coming over there as it gone increasing frequency, you come to a
certain value ν0; at this stage electrons start coming off. As you
increase the frequency further we find that electrons keep coming and
they have more and more kinetic energy as you proceed further. So we
find that the kinetic energy of the emitted for electrons increase with
the frequency, that is the third observation we have.

And then the fourth observation was that if I have the same metal and
increase the intensity of radiation which is falling on there. What is
observed thereafter is that the current continues to be there but the
magnitude of the current increases that means with increasing intensity
there is more current coming there. At the same time, the stopping
potential of these electrons remained the same that means all these
electrons which come off, they came out with the same kinetic energy-
that is the fourth observation we have. So let’s see what are the fourth
things we have seen there. The photoemission is instantaneous i.e. the
no time lag. A minimum frequency called as threshold frequency is
required. Thirdly the kinetic energy of the emitted photoelectrons
increases with frequency and lastly an increase in intensity increases
the number of electrons but their kinetic energy does not change. So
there are four significant observation vis-à-vis our experiment of
photoelectric effect.

Let’s see what classical mechanics tells us on these-the classical

predictions. Let’s take one by one all of these observations. The first is
that classical speaking our radiation exists as a wave o.k. and the
energy of this radiation is distributed over the whole wave. We have a
small electron target over there. So what classical mechanics says -we
have a small target- say electron over here. This is the wave coming
there. Now what it says is that the coming wave is coming with certain
amount of energy, this electron needs certain energy to come out from
there. So as this wave is coming this (electron) keeps on absorbing
energy and when sufficient amount of energy comes to this it will come
off. That means the electron should not be emitted immediately it
should come out after certain amount of time. There should be a time
lag according to classical mechanics i.e. the first observation or the first
prediction of classical mechanics is that there must be a time lag
between throwing the light on metal at electrons coming from there.
You remember that experimentally we have observed just opposite of
that. The second prediction, now second prediction is that since we
have the electron and my radiation is coming. The classical mechanics
presumes or suggests that no matter what wavelength I take what
frequency I take. As long as suppose I take say a low frequency
radiation, so the wavelength is high radiation coming there and it just
low, its coming there it gets absorbed to certain extent, maybe I have
to pass this radiation for long time and when the enough energy is
there it (electron) will come off. If I take higher energy one it will come
out faster. That’s all. The only thing is that there is no need for any
threshold frequency that means the electron should come out
irrespective of what is the wavelength or what is the frequency of
radiation used for the purpose. That is a second prediction from our
classical mechanics again in contradiction with the experimental
observation.
Thirdly if I increase the amplitude that means if I increase the intensity
basically I am increasing the amplitude. What it means is a higher
intensity radiation means that this radiation has got a higher amplitude.
Let’s take an example, suppose you are standing on the seashore, and a
small wave comes- a ripple comes, it’s just comes to you, hits you and
that’s all matter ends thereafter nothing happens to you. But as against
that suppose a large wave comes with large amplitude with lot of
energy in that, that can even knock you off the feet o.k. So you will be
thrown off from the seashore. So that is what exactly is expected from
our, this phenomenal over here. If I increase in intensity what is
expected is that if a high intensity radiation is coming the electron will
be knocked off and it will have high kinetic energy whereas what we
experimentally observed was that the kinetic energy of electrons as it
came off on increasing the intensity had no change, it came out with
the same kinetic energy because the kinetic energy depended only on
the frequency of radiation and not in the intensity.

So let’s again see what we experimentally observed and what is

classical prediction over there. Experimentally observed there is no
time lag, classical prediction is there must be a time lag. Second
experimentally observation was that we need a minimum frequency
called as threshold frequency, classical prediction does not look
forward to any threshold frequency. Thirdly the kinetic energy of the
emitted photon increases with frequency whereas classical prediction is
that kinetic energy should depend on intensity and not on frequency.
And fourthly increasing intensity increases number of electrons but
kinetic energy is the same whereas classical prediction is the increase in
intensity should give faster electrons and not more electrons. We find
that all the four counts experimental observations and the classical
predictions do not match. That is a second instance we are saying and
what you find from here is that the predictions from classical mechanics
are not in agreement with the experiment. That is in other words we
can say the classical mechanics is inadequate to explain the results of
photoelectric effect and a successful emission of photoelectric effect
was given by Albert Einstein in 1905.

Summary
Let’s sum up what we done today. What we done today is we started
with understanding what is a basic premise of classical mechanics and
on the basis of that how comfortable we are in explaining the
macroscope observations what we have with us and thereafter having
established that classical mechanics works fairly well for macroscopic
system. We came down to two experiments particularly: (1) blackbody
radiation and (2) a photoelectric effect and on the basis of these two
experiments we are able to see the experimental observations what we
had and the theoretical predictions from classical mechanics do not
match. That means the classical mechanics happens to be inadequate in
explaining the results of these experiment.

In my next lecture I will take up three more cases one is the anomalous
heat capacity of solids, second is atomic line spectrum and thirdly
Compton’s effect to reemphasize this assertion of mine that classical
mechanics is inadequate in explaining certain experimental
phenomenon and once have we done that in the later lecture may be
the third lecture we will try to find out a solution to this that means we
bring in the concept of quantization and see how does this get over this
inadequacy of classical mechanics and does explain all these results
fairly well.