Basic principles of quantum mechanics, G.

Jeschke, SS 2003

2. Schrdinger equation. Particle in a 1D box

The Schrdinger equation. A Particle in a one-dimensional box

As we have seen, the behavior of quantum particles cannot easily be understood intuitively. It is necessary to use a strict mathematical formulation of the problem at hand, to derive equations for the state of the system and its evolution in time, and to interpret these equations in terms of their physical meaning. This is an elaborate work even for such a simple system as a hydrogen atom. Therefore, we start with an even simpler system- one particle in a one-dimensional box- to obtain a basic understanding how problems are solved in quantum mechanics. In this system we shall already encounter several phenomena such as energy quantization, stationary states, and bound states that are also relevant for atoms and molecules. 1 The wavefunction as a description of a quantum object If we cannot determine the position and momentum of a microscopic object at the same time, we cannot predict its trajectory according to Newtonian mechanics. Clearly, we need a different description of such quantum objects that is different from classical Newtonian mechanics to predict atomic and molecular structures, or in general, the outcome of any experiments on quantum objects. This description will be necessarily abstract, as observations on quantum objects are fundamentally uncertain. The very act of observation interferes with the state of the observed object! This is in conflict with our everyday experience of observing things and processes and with our (naive) view of reality. Thus, we cannot picture quantum objects and we cannot strictly derive the behavior of quantum objects from the known behavior of waves and particles. For this reason we first postulate a few basic principles and examine if the consequences of these postulates agree with experimental facts. Quantum mechanics was developed in this way by in 1925 by Heisenberg (matrix mechanics) and 1925/26 by Schrdinger (wave mechanics). The two approaches use different mathematics, but provide an equivalent description of quantum objects as was proved rigorously by von Neumann in 1931. In this lecture we restrict ourselves to Schrdingers approach, which is more convenient for quantum chemistry. We start with the most simple object we can have. This is a single particle moving in only one dimension along the x coordinate. At time t we characterize the state of this quantum-mechanical system by a wavefunction . This wavefunction is the quantum-mechanical equivalent

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2. Schrdinger equation. Particle in a 1D box

for the characterization of a classical particle by its position and momentum. In general, the wavefunction depends on time and on the coordinates of all particles, i.e., = ( x, t ) for our one-dimensional one-particle system. We describe the environment of our system by the potential V ( x, t ) , i.e., by the potential energy of the particle as a function of x and t. In addition, the particle may have kinetic energy. The quantum mechanics of this simple system involves only two problems: (1) Determine the possible states and, in particular, the state with minimum energy for a given time-independent potential V(x). (2) Give an equation of motion that describes how the state of the system changes with time for a given potential V ( x, t ) . The solutions of these two problems should be given in a form that is useful for physical interpretation. In other words, we should have some procedure to predict the outcome of experiments from ( x, t ) . 2 The Schrdinger equation determines the wavefunction and its dynamics We postulate the equation of motion as

2 h h ------ ( x, t ) + V ( x, t ) ( x, t ) . -- ( x, t ) = 2m x 2 i t

(2.1)

This is the time-dependent Schrdinger equation. The right-hand side of the equation can be computed from the present state ( x, t ) of the system and the left-hand side is the first derivative of the wavefunction with respect to time multplied with a constant. If we know the wave function at time t0, we can predict the wavefunction at any time in the future by integrating this equation. The wavefunction in turn provides us with the probability

( x, t ) 2 dx

(2.2)

for finding the particle in the range between x and x + dx . Because of the uncertainty principle, we can only predict a probability. We usually cannot claim that the particle is at a certain place at a given time. Note that for a complex function we have ( x, t ) 2 = ( x, t ) ( x, t ) , where

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2. Schrdinger equation. Particle in a 1D box

the asterisk denotes the complex conjugate. This was postulated by Born shortly after Schrdinger published his equation. To find the possible states ( x, t ) for a time-independent potential V ( x ) , we start from the time-dependent Schrdinger equation which now reads

h h2 2 ( x, t ) + V ( x ) ( x, t ) -- ( x, t ) = -----2m x 2 i t

(2.3)

and try to get rid of the time-dependence. This can be done by using a product ansatz for the wavefunction

( x, t ) = f ( t ) ( x ) .

(2.4)

The product ansatz has the additional advantage that the results can be interpreted more easily, as we shall see later. The partial derivatives that we need in eqn (2.3) are ( x, t ) = d f ( t ) ( x ) and ( x, t ) = f ( t ) d ( x ) . Substitution into eqn (2.3) gives 2 t dt x d x2
2 h h2 d -- ( x ) ---- f ( t ) = ------ f ( t ) d ( x ) + V ( x )f ( t ) ( x ) dt 2m i d x2 2 2

(2.5)

and by dividing by f ( t ) ( x ) we obtain h 1 h2 1 d 2 (x) + V(x) . -- ------- d f ( t ) = ------ ----------- 2m ( x ) d x 2 i f(t )dt

(2.6)

As the left-hand side (LHS) does not depend on x and the right-hand side (RHS) does not depend on t, they must equal a constant, which we call E . Note that the constant has dimensions of energy, since the potential V has dimensions of energy. By equating the two sides separately to E we obtain two simple differential equations. From the LHS we find

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2. Schrdinger equation. Particle in a 1D box

df ( t ) ----------- = iE dt . ---f( t) h Integration with respect to t yields

(2.7)

iE ln f ( t ) = ---- t + C , h where C is the constant of integration. With the new constant A = e C we obtain

(2.8)

f ( t ) = Ae

iEt h

(2.9)

As we are interested in ( x, t ) = f ( t ) ( x ) , the constant factor A can as well be included in ( x ) , so that we can write the solution in the form of eqn (2.4) as

( x, t ) = e

iEt h

(x) .

(2.10)

We do not know if all solutions of the time-independent Schrdinger equation have this form, since by making the product ansatz we have possibly excluded other solutions. However, if the potential V does not depend on time there are such solutions and they correspond to states with constant energy E. The functions ( x ) are solutions of the time-independent Schrdinger equation

h2 2 ------ d ( x ) + V ( x ) ( x ) = E ( x ) , 2m d x 2

(2.11)

which is obtained by equating the RHS of eqn (2.6) to the constant E and multiplying by (x). The observable of interest in the present problem is the probability density ( x, t ) 2 that characterizes the distribution of the particle along the x coordinate at a given time (see eqn (2.2)). Using eqn (2.10) we have iEt h iEt h iEt h ( x) ] e ( x) = e ( x )e ( x) . (2.12)

( x, t ) 2 = [ e

iEt h

= ( x ) ( x ) = ( x ) 2

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2. Schrdinger equation. Particle in a 1D box

This means that the probability density does not depend on time. The states of the form of eqn (2.10) are thus stationary states and for many purposes (x) can be used instead of the complete wavefunction ( x, t ) .1 The remaining lectures of this course are concerned solely with the time-independent Schrdinger equation and with stationary states. This is sufficient for almost all of quantum chemistry, only in spectroscopy we have to deal with time-dependence of the external potential. We shall thus refer to eqn (2.11) as the Schrdinger equation and to as the wavefunction. The Schrdinger equation has two unknowns, E and . For a given E, it is an inhomogeneous linear differential equation. This differential equation is usually subject to boundary conditions for that are related to the physics of the system or its environment. Boundary conditions result in discrete stationary states, i.e., only certain values of the energy E are allowed as we shall see in the following treatment of a particle in a one-dimensional box. 3 The Particle in a One-Dimensional Box Before we can see how the Schrdinger equation is solved we have to specify the potential V and the boundary conditions for the wavefunction . For simplicity, we assume that the potential is zero in the range from x = 0 to x = l and infinite outside this range (Fig. 2-1). This model provides some insight into the UV/vis bands arising from the excitation of electrons distributed over a chain of conjugated bonds with length l. V(x) I x=0 II x=l

III x

Fig. 2-1: Potential energy function V(x) for the particle in an one-dimensional box.

The probability density, and hence , must be zero in regions I and III, as the energy of the particle is finite. For region II with V = 0 the Schrdinger equation (2.11) simplifies to

1. The time-dependence corresponds to only a change of the phase of the wavefunction, not its amplitude.

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2. Schrdinger equation. Particle in a 1D box

h2 d 2 ( x ) = E II ( x ) , -----2m d x 2 II which can also be written as

(2.13)

d II d x2

2m + ------ E II = 0 . h2

(2.14)

This is a linear homogeneous second-order differential equation with constant coefficients. We see that a linear combination of and its second derivative is zero everywhere. This suggests solutions of the form II = e , since the derivative of an exponential function is an exponential function times a constant. Making this substitution, we obtain
sx

2 sx 2m - sx s e + ------ Ee = 0 . 2 h

(2.15)

Thus, we have

s + 2mE h 2 = 0 ,

(2.16)

s = i 2mE h .

(2.17)

Any linear combination of solutions to a linear homogeneous differential equation is also a solution of this differential equation. Therefore, the general solution of eqn (2.13) is

II = c 1 e with =

i 2mEx h

+ c2 e

i 2mEx h

= c1 e + c2 e

(2.18)

2mEx h . As e

= cos + i sin , we can also write this as

II = A cos [ 2mEx h ] + B sin [ 2mEx h ] , where A and B are constants that have to be determined from the boundary conditions.

(2.19)

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2. Schrdinger equation. Particle in a 1D box

As is zero in regions I and III, we have boundary conditions ( 0 ) = 0 and ( l ) = 0 , if we require that is continuous. Continuity is a general property of physically reasonable wavefunctions. Thus, II ( 0 ) = A cos [ 0 ] + B sin [ 0 ] = A = 0 . With A = 0 we have for the second boundary condition

(2.20)

II ( l ) = B sin [ 2mEl h ] = 0 .

(2.21)

We cannot have B = 0 , as this would mean ( x ) 0 , i. e., the particle would be missing. Therefore,

sin [ 2 2mEl h ] = 0 .

(2.22)

As the sine function has zero crossing for arguments n, where n is a natural number, we find

2 2mEl h = n ,

(2.23)

n2h2 E = ----------- . 8ml 2

(2.24)

The case E = 0 is special, as the wavefunction would again be 0 , i. e., there would be no particle. Hence, only n = 1, 2, 3, are allowed. The state with lowest energy (n = 1) is the ground state, all other states are excited states. Note that this quantization of the energy is a result of imposing the boundary conditions to . In a classical picture (billiard ball between two walls), any nonnegative value of the energy would be allowed. Zero energy, for instance, would correspond to a ball at rest. A quantum particle cannot be at rest, since otherwise both p = 0 and x would be precisely known at the same time, which violates the uncertainty relation. By substituting eqn (2.24) in (2.21) we obtain the wavefunctions

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2. Schrdinger equation. Particle in a 1D box

nx ( x ) = B sin -------- for 0 x l ; ( x ) = 0 elsewhere . l

(2.25)

To fix the constant B, we use the normalization requirement that the probability to find the particle anywhere in the box must be unity
l l 2

dx =

II
0

dx =

II II dx
0

= 1 .

(2.26)

Hence,
l

nx l B 2 sin2 -------- dx = B 2 -- = 1 , l 2
0

(2.27)

B =

2l .

(2.28)

Only the absolute value of B can be determined. In fact, B may be complex. If we settle for a rela positive number,1 the final solution is

(x) =

2 sin nx for 0 x l ; ( x ) = 0 elsewhere . -- -------- l l

(2.29)

The five lowest energy levels and the wavefunctions corresponding to the three lowest energy levels are shown in Fig. 2-2. For the states with n > 1 the wavefunctions feature zero crossings, which are called nodes. More precisely, there are n 1 nodes where the probability to find the particle vanishes.

1. The uncertainty about the phase is in fact contained in f ( t ) .

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2. Schrdinger equation. Particle in a 1D box

a
E (eV)
40 30

b
5

n=1
10
9

n=2

n=3

n=5

||

n=4
20
6

0 10
4

n=3
10 0

0 -6 0 r () 6 0 r () 6 0 r () 6

n=2 n=1

Fig. 2-2: Energy levels and wavefunctions for an electron in a one-dimensional box with a length of 0.5 nm (5 ). a) Energy levels of the five states with lowest energy. b) Wavefunctions (bottom row) and probability densities (top row) of the three states with lowest energy.

Another common property of wavefunctions can be recognized by generalizing the normalization integral, eqn (2.26), to the overlap integral of two different wavefunctions

n i x n j x 2 2 l - i j dx = -- sin ---------- sin ---------- dx = -- -- sin ( n i ) sin ( n j ) dx , l l l l

0 0

(2.30)

where = x l . As sin sin = ( 1 2 ) [ cos ( ) cos ( + ) ] , we find

i j dx = 0,

ij .

(2.31)

This is the condition for two wavefunctions i and j being orthogonal. Usually, this is combined with eqn (2.26) to the condition of wavefunctions being orthonormal

i j dx

= ij ,

(2.32)

where ij is the Kronecker delta with is zero (0) for i j and unity (1) for i = j .

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2. Schrdinger equation. Particle in a 1D box

The Particle in a Rectangular Well. Tunneling. In the following, we consider the somewhat more realistic situation where the walls of the

box have finite height (Fig. 2-3). The mathematical treatment is omitted, it can be found in Levines book. We notice that the wavefunction of the ground state and the first excited state now extend outside the well into the wall. This is despite the fact that the energy of these two states is lower than the height of the wall. In classical physics, it would be forbidden that a particle can be found in a region of space where its potential energy is higher than the total energy. That a quantum object can be found in such a region is a direct consequence of the uncertainty relation for energy and time, eqn (1.4).

Fig. 2-3: Particle in a one-dimensional rectangular well. a) Potential energy. b) Ground-state wave function. c) First excited-state wavefunction. Adapted from Levine, Quantum Chemistry.

Still the wavefunctions and probability densities of the ground state and first excited state approach zero for x and x . Such states are called bound states. There are also unbound states where the energy is higher than the height of the wall, E > V 0 . In this case the wavefunction does not approach zero for x and x and thus cannot be normalized. The same phenomenon occurs for electrons of an atom or molecule if they are excited to energies that are higher than the ionization energy. These electrons than become free electrons. The fact that a particle can penetrate into a region of space that would be classically forbidden gives rise to the quantum phenomenon of tunneling. Assume that you want to contain an electron in a box with walls of finite height and thickness (Fig. 2-4). You place the electron in the allowed region I. However, the wavefunction for the case of a rectangular box with walls of finite height (Fig. 2-3) leads you to suspect that the electron can penetrate into the forbidden regions. In particular, there should also be a certain probability to find the electron in allowed region II. This means that the electron has escaped its containment! Quantum-mechanical computations of this problem and of similar problems show indeed that a quantum object can cross

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2. Schrdinger equation. Particle in a 1D box

an energy barrier even if its energy is lower than the barrier height. Such quantum tunneling becomes increasingly important for objects with decreasing classical behavior, i.e., with decreasing mass of the particles involved. Chemically relevant examples of tunneling are the inversion of the pyramidal structure of an NH3 molecule and the rotation of methyl groups at low temperatures. Tunneling also contributes to the rate of reactions where hydrogen atoms are transferred. Finally, tunneling of electrons between the tip of a metal wire and the surface of an electrically conducting sample is used for imaging the surface of the sample in the scanning tunneling microscope (STM).

forbidden

V0

allowed I

forbidden

allowed II

Fig. 2-4: Potential energy and classically allowed and forbidden regions for a particle in a one-dimensional box of finite height and thickness.

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