PM575C9DA868PRINCIPLES OF QUANTUM MECHANICS The motion of macroscopic particles can be observed either directly (or) through microscope.

Classical mechanics can be applied to explain their motion. But when we consider motion of micro particles such as electrons, protons, classical mechanics fails. But their motion can be explained by Quantum mechanics. Max Planck proposed quantum theory at the beginning of 20th century. 1. Waves and particles: To under stand the concept of dual nature one should have to know the characteristics of particles and waves. Wave: It is difficult to understand the concept of a wave, since it is not a physical quantity and physically it cant be seen. A wave can be simply defined as spreading out of a disturbance in a medium in all directions uniformly. It cannot be confined to a part (or) region i.e. it is not possible to say that the wave is present here (or) there. A wave is characterized by Particle: It is easy to understand the concept of particle, since it is a physical quantity and can be perceived physically. A particle has a definite mass and occupies a definite space. When a force is applied on it, it moves in the direction of force from one point to another. A particle is characterized by Mass Velocity Momentum Energy Wavelength Frequency Wave velocity Amplitude Phase Intensity

The particle nature of radiation can be observed in photoelectric effect and Compton Effect. The wave nature of radiation is seen in interference and diffraction experiments. Hence radiation is capable of exhibiting dual nature. But it is not possible to exhibit both the wave nature and particle nature at the same time. 2. de-Broglie Hypothesis: De-Broglie in 1924 extended the wave-particle duality to material particles like electrons, protons, and neutrons can behave as wave. According to his hypothesis, a moving particle is associated with a wave with a certain wavelength is known as de Broglie wave or matter wave. His hypothesis is based on the fact that nature loves symmetry. That is if radiation exhibits dual nature of wave and particle; matter will also exhibit the same dual nature. According to de-Brogile a moving particle, whatever its nature, has wave properties associated with it. He proposed that the wavelength associated with any moving particle of momentum p is given by h p h mv

= =

Such waves associated with the matter particles are called matter waves or de-Broglie waves. De-Broglie indicated that an electron in a Bohr orbit moving around the atom's nucleus would possess a wavelength of the right dimension to form standing waves. He Imagine the orbit as a pilot wave. De Broglie used his matter-wave hypothesis to explain quantization of atomic orbital.

The n full wave lengths of a de Broglie electron wave fit around the circumference of the electrons circular orbit. That is n = 2 r 2.1 Expression for de-Broglie wavelength:According to the Plancks and Einstein theories the energy of a photon whose frequency can be expressed as

E = h ------------------- (1)
Where h is the Plancks constant. According to Einsteins mass energy relation m = c From eq (1) and (2)
h =c m
h c
2

------------------- (2)

= m c

h =
m c
For electron we put v in place of c

------------------------------ (3) This is called de-Broglies equation. The wave length of the matter wave is inversely propositional to its momentum. Wave length of the matter wave in terms of potential V:The energy of the electron in terms of potential can expressed as
E = eV ---------------------------------- (4)

The kinetic energy of an electron is

E= From equation (4) and (5)

1 2 mv --------------------------------- (5) 2 1 2 mv 2 1 2 2 mv 2

eV =

Multiplying by m in either sides of the equation meV =

P = 2meV Now from equation (3) h 2meV 6.625 1034 2 9.11031 1.6 1019 V 12.27 1010 = m V

Substituting the value of h, m and e, the wavelength associate with electron

Wave length of the matter wave in terms of energy E:If E is the kinetic energy of the electron then E= = = 1 2 mv 2

m2v2 2m p2 2m p2 2m ( p = mv )

E= From above equation we get

p = 2mE Now from de Broglie hypothesis the wave length of the matter wave in terms of energy is

h 2mE

Properties of matter waves:1. The wave length of the matter wave is inversely proportional to the mass of the particle. The larger the mass of the particle, the shorter will be the wave length vice versa. 2. The wave length of the matter waves is is inversely proportional to the velocity of the particle. 3. The matter waves are produced whenever the matter particle (charged or uncharged) is in motion where as the electromagnetic waves are produced whenever charged particles are in motion. This property shows that the matter waves are not electromagnetic waves. 4. The velocity of the matter wave is not constant. The velocity of the matter wave depends on the motion of a material particle. The velocity of the electromagnetic radiation is constant. 5. The wave nature of matter introduces an uncertainty in the location of the position of the particle. 6. The velocity of the matter wave is greater than the velocity of light. Equating the Einsteins equation and Plancks equation we, get E = hv E = mc 2 hv = mc 2 v= mc 2 h

The wave velocity is w = velocity wavelength w= Substituting = h mv mc 2 h c 2 w= = h mv v c2 w= v mc 2 h

As the particle velocity v cannot exceed velocity of light c , w is greater than the velocity of light c .

3. Davisson and germer experiment:The first practical evidence for the matter waves was given by C.J.Davisson and L.H.Germer in 1927. This was the first experimental support for De-Broglies hypothesis. Experimental arrangement: -

1. The experimental arrangement is shown in fig. it consists of three parts; they are electron gun, target set up and circular scale arrangement. The whole experiment is kept in vacuum. 2. The electron gun produces a fine beam of electrons of a required velocity. It consists of filament (F), low tension battery (LTB), high tension battery (HTB) and pin holes provided in the cylinder (C). 3. When tungsten filament F is heated by low tension batteries (LTB) then electrons are produced. These electrons are accelerated to a required velocity by applying sufficient potential through the high tension battery (HTB), across the cylinder C.

4. The accelerated electrons are collimated into a fine beam of pencil by passing them through a system of pin holes provided in the cylinder C. 5. The target set up help to get diffraction pattern. The target is typically nickel crystal. The fast moving beam of electrons from electron gun is made to incident on the nickel target, which can be rotated about an axis perpendicular to the plane of the diagram. 6. The electrons are reflected in all possible directions by rows of a atoms in the surface planes, which acts as a diffraction grating. 7. In the circular scale arrangement, an electron collector is fixed to a circular scale which can collect the electrons and can move along the circular scale. The electron collector is connected to a sensitive galvanometer to measure the intensity of electron beam entering the collector. Calculation of the wavelength associated with electrons:When a potential of 54v is applied the first order diffraction maximum is observed at angle of 500 between incident and reflected rays. It can be observed in the plot of variation of number of scattering electrons with the angle of diffraction as 650. The inter planar spacing (d) of nickel crystal is 0.091nm, which is measured by the xray diffraction method.

Applying Braggs law 2d sin = n We know

= 650 d = 0.091nm n =1
Now from the Braggs law equation

= 1.648A0
The de-Brogile wavelength associated with the electron, when a potential difference of 54v is applied. According to de-brogile wave length 12.26 12.26 = = 1.66 A0 V 54

The wavelength of the electron beam calculated from Braggs law and de-Brogiles equation are in good agreement. Hence the wave nature of the particle is proved experimentally. The drawback of this experiment is that whether the diffraction pattern formed is due to electrons (or) electromagnetic radiation generated by fast moving electrons are not known.

4. G.P Thomson experiment:In G.P Thomson experiment proved that the diffraction pattern observed was due to electrons but not due to electromagnetic radiation produced by the fast moving changed particles. Experimental arrangement:G.P Thomson experimental arrangement consists of six parts they are 1. Cathode 2. A fine hole metal block 3. Gold foil 4. Photographic plate

1. The experimental set up is shown in the above figure. The cathode C is heated by a low-tension battery and it emits electrons. The emitted electrons are accelerated by an accelerating potential of nearly 50 kV. 2.
8

The accelerated electrons are passed through a thin slit, S, and the emergent electron beam from the slit is made to fall on a gold thin foil G of thickness 10m.

3. The diffraction pattern is recorded in a photographic plate P. When the plate is developed a symmetrical pattern consisting of concentric rings about a central spot, is obtained. The whole apparatus is kept highly evacuated. 1. When the cathode rays in the discharge tube are deflected by magnetic field, the entire pattern on the screen S is found to shift. 2. Thus the pattern is confirmed as due to diffracted electrons and not due to secondary X-rays, generated by the electrons going through the foil. Further, on removing the film F the pattern disappears, showing that the presence of the film is essential. 3. If the electrons behaved as particles, the foil should scatter the electrons through a wide angles. This experiment demonstrates that the electron beam behaves as waves, since diffraction patterns can be produced only by waves.

Calculation of the wavelength associated with electrons: -

From fig OA is the center of the ring, Q is the where the electron strikes a particular point on the gold foil. QO is the distance between the gold foil and the photographic plate and is represented by L. according to Braggs law is
n = 2d sin

From fig

r = tan 2 2 L

=
Now Braggs law can be written as

r 2L r 2L

n = 2d = 2d

rd nL

From the above expression, the wavelength of electrons can be calculated.

Heisenbergs uncertainty principle:In 1927 Heisenberg proposed a very interesting principle known as uncertainty principle as a consequence of the dual nature of the matter. Statement:It is impossible to determine precisely and simultaneously the value of the members of a pair of physical variables which describe the motion of an atomic system. Such pairs of variables are called canonically conjugate variables. According to uncertainty principle if we obtained a perfect knowledge of the position of an electron we have no way of knowing its momentum, and the reverse. If particle is moving based on classical mechanics, at any instant we can find its position and momentum. In wave mechanics, we regard a moving particle as a wave group. The particle that corresponds to this wave group may be located anywhere within the group at any given time. Of course, in the middle of the group, the probability of finding the particle is more but the probability of finding the particle at any other point inside the wave group is not zero. Narrow the wave group higher will be the accuracy of locating the particle. At the same time, one cannot define the define the wavelength of the wave accurately when the wave group is narrower. Since measurement of particles h momentum = also becomes less accurate. mv On the other hand when we consider a wide wave group, wavelength can be well defined and hence measurement of momentum becomes more accurate, at the same time, since the width of the wave group is large, locating the position of the particle becomes less accurate. Thus we have uncertainty principle. If x and p are the uncertain in the position and momentum measurements then, according to uncertainty principle

x p

h 4

Thus the uncertainty principle is a direct consequence of the wave nature of particle.

Another form of the uncertainty concerns energy and time. If the energy is emitted in the form of electromagnetic waves, we cannot measure the frequency v of the waves accurately in the limited time available. Since v 1 t

Hence the corresponding uncertainty in energy E is E = hv And so Or E h t

E t h

A more precise calculation based on the nature of wave group modifies this result to E t h 4

This gives uncertainty in the measurement of an energy and time of a process.

Schrdinger wave equation:In 1926 Schrdinger presented his famous wave equation as a development of de Broglie ideas of the wave properties of matter. The Schrdingers equation is the fundamental equation of quantum mechanics. It is the differential equation for the debroglie waves associated with particles and describes the motion of the particles. Schrdinger introduced a mathematical function which is the variable quantity associated with the moving particle, and is a complex function of the space coordinates of the particle and the time. is called wave function as is characterizes the waves associated with the particle. If a particle of mass m moving with a velocity v is associated with group of waves. Let us consider a simple form progressing wave traveling in positive x-direction as time t is

= 0 sin ( t kx ) ------------------ (1)

Where

= (x,t) and
0 is the amplitude.

Differentiating partially with respect to x twice, 2 = k 2 0 sin ( t kx) 2 x = k 2 2 2 + k 2 = 0 (Or) -------------------- (2) x 2 4 2 + 2 = 0 -------------------------- (3) x 2 Since k= 2 .

Equation (2) is the differential form of the classical wave equation. Now we incorporate de Broglie wavelength expression obtain 2 4 2 m2 v2 + = 0 ----------------------------- (4) x 2 h2

h into equation (3). Thus we mv

The total energy E of the particle is sum of its kinetic energy K and potential energy V, i.e. E = K + V ------------------------------------ (5) and K = 1 2 mv -------------------------------------- (6) 2

m 2v 2 = 2m(E V ) ----------------------------------- (7) Substituting equation (7) in equation (4) 2 8 2 m (E V ) + =0 x 2 h2 In quantum mechanics, the value h occurs most frequently. Hence we denote 2

h=

h . Using this notation, we have 2 2 2m (E V ) + = 0 ------------------------------ (8) x 2 h2 Where = (x,t) . 2 2 2 2m (E V ) + + + = 0 ------------------------- (9) x 2 y 2 z 2 h2

Using Laplacian operator, 2 = 2 2 2 + 2 + 2 -------------------------------- (10) x 2 y z

The equation (10) can be written as

2 +

2m (E V ) =0 h2

This Schrdinger time independent wave equation.

Physical significance of the wave function ( ): The probability that a particle will be found at a given place in space at a given instant of time is characterized by the function ( x, y, z , t ) .It is called the wave function. This function can be either real or complex. A satisfactory interpretation of the wave function associated with a moving particle was given by Born in 1926. He postulated that the square of the magnitude of the wave function

(or) * evaluated at a particular point at any instant

represents the probability of finding the particle at that point.

is called the probability density and is the probability amplitude.

According to this interpretation, the probability of finding the particle within an element of volume d (dxdydz ) is d , since the particle is certainly somewhere in space. So the integral of d over all space must be unity, that is
2 2

d = 1

The wave function that obeys this equation is said to be normalised. There are certain limitations to take as a solution for the Schrdinger wave equation, they are (1) must be finite every where: if for instance is infinite for a particular point, the same would be true for the wave function * . It would mean an infinitely large probability of finding the particle at that point. This would violate the uncertainty principle. There fore must have a finite or zero value at any point.

(2) must be single-valued : - if has more than one value at any point, it would mean more than one value of probability of finding the particle at that point which is obviously ridiculous. (3) must be continuous and have a continuous first derivative every where:It necessary for the Schrdinger equation is that d 2 must be finite every where. This dx 2

can be so only if

d d has no discontinuity at any boundary. So is a continuous dx dx

function then is also continuous across the boundary. Particle in one dimensional potential box :Consider a particle moving inside a box along the X-direction. The particle is bouncing back and forth between the walls of the box. The box has potential barriers at X=0 and X=L i.e. the box is supposed to have walls of infinite height at X = 0 and X = L. the particle has mass m and its position x at any instant is given by 0 < X< L. The potential energy V of the particle is infinite on both sides of the box. The potential energy V of the particle can be assumed to be zero between X = 0 and X = L.

In terms of the boundary conditions imposed by the problem, the potential function is

V = 0 for 0 < X < L

V = for X 0

V = for X L The particle cannot exist outside the box and so its wave function is 0 for X 0 and X L . Our task is to find what is within the box i.e. in between x = 0 and x = L. Within the box, the Schrdingers equation becomes d 2 8 2 m + 2 E = 0 ----------------------- (1) dx 2 h 8 2 mE Putting = k 2 , the equation becomes 2 h d 2 + k 2 = 0 ------------------------------ (2) 2 dx The general solution of equation (2) is

= A sin kx + B cos kx -------------------- (3)

The boundary conditions can be used to evaluate the constants A and B in equation (3) .

= 0 at x = 0 and hence B = 0 = 0 at x = L . Hence 0 = A sin kL

Since A 0 , kL= n where n is an integer or k = Thus n L

n ( x) = A sin

n x ----------------------------- (4) L

The energy of the particle

k 2 h2 h 2 n2 2 En = 2 = 2 2 ----------------------------- (5) 8 m L 8 m
En = n 2h 2 ---------------------------------- (6) 8mL2

For each value of n, there is an energy level and the corresponding wave function is given by Equation (4). Each value of En is called an eigen value and corresponding n is called wave function. Thus inside the box the particle can only have discrete energy values specified by equation (6). Note that particle cannot have zero energy.

The value of A in equation (4) can be obtained by applying normalization condition. Since the particle is inside the box of length L, the probability that the particle is found inside the box is unity.
L

* 0

dx = 1

L n x A2 sin 2 =1 0 L

A2

2n x 1 cos L dx=1 2

A2 A=

L =1 2 2 L 2 n x sin L L

The normalized wave functions of the particle = n =

The normalized wave functions 1 , 2 and 3 and corresponding probability density functions n are plotted in fig.
2