Introduction to Quantum Mechanics Schrodingers Equation

Instructor: Gautam Dutta

DA-IICT winter 2012

Schrodingers Equation

Schrodingers Equation

Particles are associated with waves. Waves of what? Electric eld, Magnetic eld, mass density... Schrodinger: Probability waves P (x) = e
2i (pxEt) h

=e

i (pxEt)

(1)

h Here = 2 . Can probability be negative? Experimentally these probabilities must form an interference pattern.

Electromagnetic waves have amplitude E which can be both positive

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Schrodingers Equation

and negative but intensity that we measure is |E|2 We denote the wave amplitude by (x) given by Eq.1 and the non-negative probability P (x) will be given as P (x) = |(x)|2 = (x)(x) (x) can be +ve or -ve. We allow it to be complex in general. We need such a quantity to produce the interference eect. (x) is called the probability amplitude and P (x) is the probability density for the particle to be found at x.

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Schrodingers Equation

Since it is certain to nd the particle somewhere between and +, it is obvious to expect the following normalization for

dx = 1

What is the Equation that governs the evolution of Consider i (pxEt) =e . Then 2 2 2 = p2 x Also i = E t

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Schrodingers Equation

Classically E = p /2m for a free particle. So = e the following equation

2 2 = i t 2m x2

i (pxEt)

satises

(2)

If the particle is under the inuence of a pottential V (x) then p2 E= +V 2m An appropriate equation for the wavefunction of such a particle would be 2 2 + V (x) (3) = i 2 t 2m x
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Schrodingers Equation

Obviously = e with a single value of E and p will not satisfy this equation. A superposition (x, t) = might satisfy. The above Equation was suggested by Erwin Schrodinger for the evolution of the wavefunction of a particle of mass m in a pottential V. It is like the Newtons Equation in Classical Mechanics. Once we solve Schrodingers Equation and nd evrything about the particle is known that is possible to be known in Quantum Mechanics. (x, t) gives the probability amplitude of nding the particle at the
[5]

i (pxEt)

f (p)e

i (pxEt)

dp

Schrodingers Equation

point x at the time t. The probability of nding the particle between x and x + dx is dx. So the probability of nding the particle between x1 and x2 is
x2

P (x1 x x2) =
x1

dx

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Schrodingers Equation

Operators: How do we get the values of physical quantities like Energy, Momentum, Position Angular Momentum etc from ?

Here we dont have a well dened position and momentum of the particle. So we cant assign values of physical quantities to the particle, like energy, angular momentum etc, which are functions of its position and momentum. But here we have states of particle dened by the wavefunctions satisfying the Schrodingers equation. The collection of all possible states of the particle constitute a vector space since the Schrodingers equation is a linear dierential equation. We can dene linear operators on this vector space. Certain states may be eigenstates of
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Schrodingers Equation

these operators. It can be shown that the eigenstates of an operator are linearly independent and they constitute a basis of the vector space. We take the example of a free particle described by the i (pxEt) . Then wavefunction = e i = p x
So the free particle states are eigenstates of the operator p = i x . Similarly as we have seen earlier these states are eigenstates of the energy operator E = i t .

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Schrodingers Equation

How do we construct the position operator? Consider the fourier transform of the spatial wave function (x) f (p) = Then (x) = p(x) = i x and f (p) = i p x(x)e
i px

(x)e

i px

dx;

(x) =

f (p)e

i px

dp

pf (p)e

i px

dp

dx
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Schrodingers Equation

We have the following pairs of fourier transforms: f (p) (x) (x) pf (p) i x i f (p) x(x) p
In the position representation, i x is the momentum operator. By analogy i p is the position operator in the momentum representation. The third fourier transform pair above suggests that in the position representation the position operator is x. So in the position representation the position operator is a multiplicative operator i.e
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Schrodingers Equation

x(x) = x(x). Every measurable physical quantity is associated with an operator. The form of the operator has to be known in a particular representation. An Operator can be a dierential form or a multiplicative form depending upon the representation we are working with. For example in the position representation the momentum operator is given by the dierential form p = i x while the position operator is given by the multiplicative form x=x If the wavefunction of the particle is an eigenfunction of an operator
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Schrodingers Equation

then it is easy to nd the physical quantity corresponding to that operator. O = o describes the state of a particle in which the value of the physical quantity corresponding to the operator O is o. E.g pe
i (pxEt)

= pe

i (pxEt)

i (pxEt) = Ee i (pxEt) Ee However in general may not be in an eigenstate of momentum and i (pxEt) dp then energy. If (x, t) = f (p)e p = f (p)pe
i (pxEt)

dp
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Schrodingers Equation

Probability density of nding the particle with a momentum p is given by |f (p)|2 = f (p)f (p). The average momentum or the Expectation value of momentum is p= Note that this is equal to Try this exercise. |f (p)|2pdp

pdx.

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Schrodingers Equation

Steady state or Stationary states If the total energy of a particle is constant in a state then its wave function (x, t) can be written as
i

(x, t) = e

Et

(x)

Substituting into Schrodingers Equation 2 2 +V 2 x 2 2 i Et i Et (x) + V (x) Ee (x) = e 2 2m x 1 i = t 2m

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Schrodingers Equation

2 2 + V (x) = E(x) 2 2m x H(x) = E(x) Where the operator

(4)

2 2 +V H= 2 2m x is called the Hamiltonian operator and equation4 is the steady state form of the Schrodinger Equation. It is an eigenvalue equation and it cannot in general be solved for any value of E and it depends upon the boundary condition. Only specic values En are allowed. These values are called the eigenvalues of the of H. The corresponding solution to the equation are labelled by n.
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Schrodingers Equation

Thus Hn(x) = Enn(x) Quantization comes naturally in Schrodingers formalism.

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Schrodingers Equation

Application of Schrodinger Equation Particle in a rigid box Consider a particle of mass m conned within a rigid box of side L. In one dimension the potential in which the particle is kept can be given as V = 0 for 0 < x < 1 V = for x 0 and x L In the region outside the box the particle cannot exist since the potential is innite. Within the box the Schrodinger Eqn is 2 = E 2 2m x
2

2 2mE = 2 2 x
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Schrodingers Equation

(x) = A sin

2mE

x + B cos

2mE

Boundary conditions: = 0 at x = 0 = B = 0 (x) = A sin = 0 at x = L.

2mE

(L) = A sin L=0 2mE = L = n n2 2 2 E= 2mL2 Normalisation:

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2mE

Schrodingers Equation

|(x)|2dx = 1 nx A sin dx = 1 L 0 2 2L A = 1 = A = 2 L Find the average value of momentum p, p2, position x, energy E
2 inf ty L 2

Find (p)2 = p2 p2, (x)2 and px

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Schrodingers Equation

Physical Interpretation of Energy Eigenfunction iE t If (x, t) = e n n(x), the particle has a xed energy En. If we have several identical systems and we measure the energy of the particle independently in each of these systems then the energy will turn out to be En.

n En

n En

n En

n En

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Schrodingers Equation

In general the particle may not be in any eigenstate. In such a case a measurement in identical systems will give dierent values but each measurement will allways give only one of the eigenvalues E1, E2, E3, .....En, ..... The same applies for any other observable O that we measure.

E4

E1

E2

E
k

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Schrodingers Equation

Let (x, t) = a11(x, t) + a22(x, t) + .... + ann(x, t) Since energy is a physical observable with real values, the energy eigenfunctions are real. The average value of the energy in the linearly superposed state (x, t) must also be real. E = =
i=1

i (x, t)dx (x, t) t

n

|ai|2Ei +
i=j

aaj Ej e i

i (EiEj )t

i (x)j (x)dx
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Schrodingers Equation

Since E must be a real number in any state, we must have

i (x)j (x)dx = 0 for Ei = Ej (x)(x)dx

is dened as the scalar product in the space of the states of the quantum system. So we conclude that eigenstates corresponding to dierent eigenvalues of a physical observable are orthogonal. We will see that the linear operators corresponding to physical observable are hermitian.

= 1 =
i

|ai|2
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Schrodingers Equation

Also E =
i

|ai|2Ei

These implies the following interpretations: We measure the energy of the system in this state. We will always get the values E1, E2...En with the following probabilities P (E1) = |a1|2 P (E2) = |a2|2 ..... = .... P (En) = |an|2 Mesurement in Quantum Mechanics
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Schrodingers Equation

Let (x) be an eigenstate corresponding to a potential V (x) with energy E. The measuring system will be some potential V (x), say the innite well potential. Then the process of measurement spontaneously throws(captures) the particle in one of the eigenstates of V (x) 1, 2,... n with probability |a1|2, |a2|2, ....|an|2. The process of measurement inherrently have to disturb the system and we cannot measure the exact value E in any measurement.

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Schrodingers Equation

V E

V
3

E3 2

E1 2 E1

Given system

Measuring system

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Schrodingers Equation

The Harmonic Oscillator

V(x)

1 2 V (x) = kx 2
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Schrodingers Equation

p2 H = + V (x) 2m 2 2 1 2 + kx = 2 2m x 2 Time independent Schrodingers Eqn: 2(x) 1 2 + kx (x) = E(x) 2 2m x 2 mk x2 (x) = e with = 2 is a solution with energy E= k 1 = m 2
2

(5)

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Schrodingers Equation

In general the solutions which are well dened are given by x2 n(x) = AnHn( 2x)e where H0(y) = 1 H1(y) = 2y H2(y) = 4y 2 2 H3(y) = 8y 3 12y H4(y) = 16y 4 48y 2 + 12 The energy in the state n(x) is En = (n + 1/2)
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Schrodingers Equation

V(x) E3 E2 E1 E
0

The wavefunction exist even in the classically forbidden region.

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Schrodingers Equation

V(x) E4
4

The wavefunction exist even in the classically forbidden region.

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Schrodingers Equation

Particle in a non-rigid box Finite potential well.

Asin(kx) +B Cox(kx)

kx

V e k(Lx)

Properties of wavefunctions 1) should be continuous 2) lim|x| (x) = 0

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Schrodingers Equation

3) ||2dx = 1 4) The rst spatial derivative of must be continuous wherever V is nite. Let us divide the whole space into three distinct regions. Region 1: < x < 0; V (x) = V0 Region 2: 0 < x < L; V (x) = 0 Region 3: L < x < ; V (x) = V0

We solve the Schrodingers Equation in the three regions and match (x) and its derivative at the boundaries of the regions. In region 2 we have 2 = E 2 2m dx
2
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Schrodingers Equation

Here the soln is 2(x) = A2e

k2 x

+ B2e

k2x

k2 =

2mE
2

where A2 and B2 are arbitrary constants to be determined from the boundary conditions. In region 1 the time independent Eqn is 2 + V0 = E 2 2m dx Here the soln is 1(x) = A1e
k1 x 2

+ B1e

k1x

k1 =

2m(E V0)
2
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Schrodingers Equation

Similarly in region 3 we have 3(x) = A3e

k3 x

+ B3e

k3x

k3 =

2m(E V0)
2

Note that k2 is imaginary, while k1 and k3 are real. As x , B1ek1x . So we put B1 = 0 As x , A3ek3x . So we put A3 = 0 So we have 1(x) = A1ek1x 2(x) = A2ek2x + B2ek2x 3(x) = B3ek3x

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Schrodingers Equation

At x = 0 we have 1(0) = 2(0). This gives A1 = A2 + B2 At x = L we have 2(L) = 3(L). This gives A2ek2L + B2ek2L = B3ek3L (7) (6)

We match the rst derivative of at the two boundaries of the well, 1(0) = 2(0) and 2(L) = 3(L) This gives A1k1 = (A2 B2)k2 B3k3ek3L = (A2ek2L B2ek2L)k2 (8) (9)
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Schrodingers Equation

From Eq.6 and Eq.8 we get k1 1 1+ A1 A2 = 2 k2 From 7 and 9 we have k2 + k1 B3 = A1e(k2+k3)L k2 k3 So we have 1(x) = A1ek1x A1 k1 k2x A1 k1 k2x 1+ e + 1 e 2(x) = 2 k2 2 k2 k2 + k1 k2L k3(Lx) 3(x) = A1 e e k2 k3
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1 k1 B2 = 1 A1 2 k2

Schrodingers Equation

A1 can be obtained by normalizing (x). k1 = k2 V0 E = i i E V0 1 E

k1 1+ = k2 k1 1 = k2 k2 + k1 = e2i k2 k3

V0 i e where E V0 i e E

tan =

V0 1 E

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Schrodingers Equation

Now 2 can be written as 2(x) = A1 At x = L, V0 cos E 2mE x

2(L) = 3(L). This gives V0 cos E 2mE L =e

i(2+ 2mE L)

(10)

The imaginary part of the R.H.S must equal to 0. So we have 2mE L 2 = n

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Schrodingers Equation

So Eqn.(10) becomes cos 2mE n L+ 2 2 = (1)

n

E V0

The energy values satisfying the above transcendental equation gives the discrete energies that the particle can have within the box. Though n can be any integer, distinct values of energy are obtained only for n = 0, 1, 2and3. Beyond this we get the cosine curves are the same and hence we get thesame energies. We can plot the E 2mE n n two graphs (1) L + 2 as a function of E V0 and cos 2 and look for their intersection. All the solutions will lie for E < V0. Beyond this the absolute value of R.H.S is greater than one and hence it cant intersect the sine or cosine curve on the L.H.S. The
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Schrodingers Equation

number of discrete energy solutions we have depends upon the height of the well V0 and the width L of the well. For every period of cosine cycle we have 2 possible energies. So for n = 0, 1, 2, 3) we will have 2 4 8 distinct energy eigenvalues. The cosine cycle completes = when E changes by 4 . So the number of discrete eigenvalues 2mL less than V0 is given by 8 V0 2 2mV0L =

4 2mL

When E > V0, the system is not bounded and we can have a valid wavefunction for the particle for any continuous value of energy.
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Schrodingers Equation

Figure 1: Eigen values of energy are given by the Eqn. cos

plot the two functions on the r.h.s and the l.h.s as a function of E . The solid curves are for even n while the dashed curves are for odd n. The intersections give the values of E . There will be no bound states beyond E = V0 .

2mE L 2

n 2

= (1)

qE

V0 .

We

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Schrodingers Equation

Examples 1. Schrodinger Equation is a linear dierential Equation. Show that if 1 and 2 are two solutions of the Schrodinger Equation then = a11 + a22 is also a solution of Schrodinger Equation. 2. The angular momentum along z direction is given by Lz = xpy ypx. Treating px and py as operators viz.. andy = i p px = i x y
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Schrodingers Equation

show that

z = i L

3. Solve the Schrodinger Equation for a free particle which is in a stationary state with energy E. Show that (x) = Ae
i

2mEx

+ Be

2mEx

is a solution to the steady state Schrodinger Equation. Find the average momentum in this state.

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Schrodingers Equation

Two and three dimensions Steady state Schrodinger Eqn: p2 (x, y, z) + V (x, y, z)(x, y, z) = E(x, y, z) 2m p2 = px 2 + py 2 + pz 2 2 2 2 + 2 + 2 (x, y, z) E(x, y, z) = 2 2m x y z +V (x, y, z)(x, y, z)
2 2

2m

(x, y, z) + V (x, y, z)(x, y, z)

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Schrodingers Equation

The momentum operator is a vector operator and is given by p = i = i + +k j i x y z

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Schrodingers Equation

Two Dimensional box

y
V=

b
V= V=0 V=

V (x, y) = 0 =

V=

0 x a and 0 y b elsewhere
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Schrodingers Equation

2 2 + 2 (x, y) = E(x, y) 2 2m x y Assume variable separable form (x, y) = (x)(y) nxx ny y (x, y) = A sin( ) sin( ) a b 2 2 n2 n2 y x E= + 2 2 a b 2m

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Schrodingers Equation

For 3-dim box of size (a,b,c) nxx ny y nz z (x, y, z) = A sin( ) sin( ) sin( ) a b c E= n2 n2 n2 y z x + 2+ 2 a2 b c 2m
2 2

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Schrodingers Equation

V=

8
c

V=0 b

V=0

V=0
a

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Schrodingers Equation

Spherically symmetric potential V (r, , ) = V (r) E.g Hydrogen atom Ze2 V (r) = 4 0r2 Harmonic Oscillator V (r) = kr2 Particle in spherically symmetric box V (r) = 0, when 0 r a = . when r > a
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Schrodingers Equation

V=

V=0 a a

Quantum Dot

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Schrodingers Equation

Schrodingers Equation in Sphericle polar co-ordinate:

2

E(r, , ) =

2m
2

(r, , ) + V (r)(r, , )

1 2 r = 2 r 2m r r 1 + 2 sin r sin +V (r)(r, , ) Comparing with the classical Equation p2 L2 E= r + + V (r) 2 2m 2mr
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1 2 (r, , ) + 2 2 2 r sin

Schrodingers Equation

1 1 2 2 sin + 2 sin sin 2 2 is given by the above Exercise: Starting with L = r p show that L operator. L2 =

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Schrodingers Equation

Separate r and the angular variables

(r, , ) = R(r)Y (, )

After rearrangement the Sch Eqn gets decoupled into r and ,

1 2 R r 2m R r r 1 1 sin 2m Y sin
2

+ r2V (r) r2E 1 2 + 2 Y 2 sin = 0

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Schrodingers Equation

Multiplying this by 2m2 gives

21

2 R r R r r

+ r22m(V (r) E) 1 2 Y + 2 2 sin = 0

1 21 sin Y sin

The angular equation can have acceptable solutions only if it is equal to a constant given by 2l(l + 1) where l is an integer. 1 sin sin 1 2 + 2 Y = l(l + 1)Y 2 sin Again by separation of
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Y (, ) are called spherical harmonics.

Schrodingers Equation

variables and it can be shown that Y (, ) = ()() = Plm()eim eim is the solution to the part of the above equation after separation into and 2 = m2 2 The periodic boundary condition along requires m to be an integer. The functions Plm() are known as Associated Lagendre polynomials given as dm Plm() = (1)m(1 cos2 )m/2 P (cos ) m l d cos
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Schrodingers Equation

Here Pl(cos ) is the Legendre Polynomial of degree l. So 0 m l. Operating Lz on (r, , ) gives (check this) z = i = m L Also L2 =
2

l(l + 1)

So the energy eigen states of any spherically symmetrical pottential z and L2 are also eigenstates of L
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Schrodingers Equation

mh

/ l(l+1) h

L 2 and L z

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Schrodingers Equation

z m=2 h 1h 0h 1 h 2 h v/l(l+1) h

l=2

1 Eg. Show that the wave function given by R(r)P1 (cos )ei, 1 i 2 and Lz R(r)P1(cos ) and R(r)P1 (cos )e are eigenstates of L operators and nd the corresponding eigenvalues. (P1(cos ) = cos )
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Schrodingers Equation

Summary

Given any system specied by a potential V ( we can nd r) energy eigen states of the system which are also called stationary states. These states are physicaly acceptable solutions to the time independent Schrodinger Equation. H(r) = E(r) The probability of nding the particle at the position r will be given as |(r)|2 |(r)|2dV = 1
allspace
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Schrodingers Equation

Physical Quantities like momentum, angular momentum etc. are replaced by their corresponding operators. A given stationary state may or may not be also an eigenstate of these operators. If they are then the physical quantity corresponding operator has a well dened value in the state given by the eigenvalue. Otherwise we can only talk about the average value of that Physical quantity. Any general state of a particle can be expressed as a linear combination(superposition) of the statinary states 1,2,3,.....,n with energy eigenvalues E1, E2, .....En respectively. = a11 + a22 + ..... + ann If we measure its energy the probability that the particle will be
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Schrodingers Equation

found in state i with energy Ei is given by |ai|2. The average energy of the particle will be given by HdV =
V i

|ai|2Ei

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