Chapter 2: The Schrödinger equation and its applications

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Outline 2.1 Wave Functions of a Single Particle. 2.2 The Schrodinger Equation. 2.3 Particle in a Time-Independent Potential. 2.4 Probability Density and Probability Current. 2.5 Scalar Product of Wave Functions; Operators. In this chapter we will discuss one of the central equation of the quantum physics. The Schrodinger equation plays the role of Newton's laws and conservation of energy in classical mechanics - i.e., it predicts the future behavior of a dynamic system. We have seen that electrons and photons behave in a very similar fashion—both exhibit diffraction effects, as in the double slit experiment, both have particle like or quantum behavior. We can in fact give a complete analysis of photon behavior—we can figure out how the electromagnetic wave propagates, using Maxwell’s equations, then find the probability that a photon is in a given small volume of space dxdydz, is proportional to |E|2dxdydz, the energy density. On the other hand, our analysis of the electron’s behavior is incomplete—we know that it must also be described by a wave function analogous to E, such that gives the probability of finding the electron in a small volume dxdydz around the point (x, y, z) at the time t. However, we do not yet have the analog of Maxwell’s equations to tell us how ψ varies in time and space. The purpose of this section is to give a plausible derivation of such an equation by examining how the Maxwell wave equation works for a single-particle (photon) wave, and constructing parallel equations for particles which, unlike photons, have nonzero rest mass. Maxwell’s Wave Equation Let us examine what Maxwell’s equations tell us about the motion of the simplest type of electromagnetic wave—a monochromatic wave in empty space, with no currents or charges present. First, we briefly review the derivation of the wave equation from Maxwell’s equations in empty space:

Where

, is speed of light. The continuity equation can either be regarded as an

empirical law expressing (local) charge conservation, or can be derived as a consequence of two of Maxwell's equations.

To derive the wave equation, we take the curl of the fourth equation, together with the vector operator identity, gives that

Meanwhile we note that, this equations shows that time dependent electric field produce magnetic field and time dependent magnetic field produce electric field. The fields are perpendicular to each others and they produce electromagnetic wave. This propety has found many technological applications. (antenna, accelerators etc). For a plane wave moving in the x-direction this reduces to

The solution to this wave equation has the form (Another possible solution is proportional to cos(kx - ωt) or cos(kx - ωt). In order to find relation between parameters we applying the wave equation differential operator to our plane wave solution and it leads to

This is just the familiar statement that the wave must travel at c. What does the Wave Equation tell us about the Photon? We know from the photoelectric effect and Compton scattering that the photon energy and momentum are related to the frequency and wavelength of the light by

Notice, then, that the wave equation tells us that

and hence E = cp.

Then if we think of the equation describing a particle (photon) it would be more natural to write the plane wave as

that is, in terms of the energy and momentum of the particle. The wave equation operator applied to the plane wave describing the particle propagation yields the energy-momentum relationship for the particle. Constructing a Wave Equation for a Particle with Mass (Optional) The discussion above suggests how we might extend the wave equation operator from the photon case (zero rest mass) to a particle having rest mass m0. We need a wave equation operator that, when it operates on a plane wave, yields Writing the plane wave function

where A is a constant, we find we can get term to the differentiation terms in the wave operator:

by adding a constant (mass)

. This wave equation is called the Klein-Gordon equation and correctly describes the propagation of relativistic particles of mass m0. However, it’s a bit inconvenient for nonrelativistic particles, like the electron in the hydrogen atom, just as E2 = m02c4 + c2p2 is less useful than E= p2/2m for this case. A Nonrelativistic Wave Equation Continuing along the same lines, let us assume that a nonrelativistic electron in free space (no potentials, so no forces) is described by a plane wave:

Note that for time dependent wave function we use capital (Psi) and time independent wave function we use We need to construct a wave equation operator which, applied to this wave function, just gives us the ordinary nonrelativistic energy-momentum relationship, E = p2/2m. The p2 obviously comes as usual from differentiating twice with respect to x, but the only way we can get E is by having a single differentiation with respect to time, so this looks different from previous wave equations:

This is Schrödinger’s equation for a free particle. It is easy to check that if has the plane wave form given above, the condition for it to be a solution of this wave equation is just E = p2/2m. Notice one remarkable feature of the above equation—the i on the left means that cannot be a real function. How Does a Varying Potential Affect a de Broglie Wave? The effect of a potential on a de Broglie wave was considered by Sommerfeld in an attempt to generalize the rather restrictive conditions in Bohr’s model of the atom. Since the electron was orbiting in an inverse square force, just like the planets around the sun, Sommerfeld couldn’t understand why Bohr’s atom had only circular orbits, no Kepler-like ellipses. De Broglie’s analysis of the allowed circular orbits can be formulated by assuming that at some instant in time the spatial variation of the wave function on going around the orbit includes a phase term of the form , where here the parameter q measures distance around the orbit. Now for an acceptable wave function, the total phase change on going around the orbit must be 2nπ, where n is an integer. For the usual Bohr circular orbit, p is constant on going around, q changes by 2πr, where r is the radius of the orbit, giving

the usual angular momentum quantization. What Sommerfeld did was to consider a general Kepler ellipse orbit, and visualize the wave going around such an orbit. Assuming the usual relationship , the wavelength will vary

as the particle moves around the orbit, being shortest where the particle moves fastest, at its closest approach to the nucleus. In this case the quantization can be written as

Thus only certain elliptical orbits are allowed. The mathematics is nontrivial, but it turns out that every allowed elliptical orbit has the same energy as one of the allowed circular orbits. This is why Bohr’s theory gave all the energy levels. Actually, this whole analysis is old fashioned (it’s called the “old quantum theory”) but we’ve gone over it to introduce the idea of a wave with variable wavelength, changing with the momentum as the particle moves through a varying potential. Schrödinger’s Equation for a Particle in a Potential Let us consider first the one-dimensional situation of a particle going in the x-direction subject to a “roller coaster” potential. What do we expect the wave function to look like? We would expect the wavelength to be shortest where the potential is lowest, in the valleys, because that’s where the particle is going fastest—maximum momentum. Perhaps slightly less obvious is that the amplitude of the wave would be largest at the tops of the hills (provided the particle has enough energy to get there) because that’s where the particle is moving slowest, and therefore is most likely to be found. With a nonzero potential present, the energy-momentum relationship for the particle becomes the energy equation

We need to construct a wave equation which leads naturally to this relationship. In contrast to the free particle cases discussed above, the relevant wave function here will no longer be a plane wave, since the wavelength varies with the potential. However, at a given x, the momentum is determined by the “local wavelength”, that is,

It follows that the appropriate wave equation is:

This is the standard one-dimensional Schrödinger equation. In three dimensions, the argument is precisely analogous. The only difference is that the square of the momentum is now a sum of three squared components, for the x, y and z directions, so

and the equation is:

This is the complete Schrödinger equation.

Time independent Schrödinger equation If the potential time independent then time part of the Schrödinger equation can be seperated by substituting

And defining

, the time dependent Schrödinger equation takes the form:

Here is named as wave function or eigen function and E is energy or eigenvalue. The equation also called eigen value equation. The equation can also be written as

Where is known as Hamiltonian operator.(we will discuss later). Therefore two forms of the Schrödinger equation:

Before going further let us mention some properties of the Schrödinger equation Schrödinger Equation Is a wave equation Probability calculation Expectation values Based on Postulates of Deals with Is applied to QM uncertainity ptinciple particle in a box Useful for calculating Wave particle duality Energy eigenvalues Free particle Barrier penetration Harmonic oscillator Hydrogen atom Nearly all QM problems consists of solving that equation.

Example: Particle in a box (Infinite well potential) As an example consider infinite well potential describes a particle free to move in a small space surrounded by impenetrable barriers. The model is mainly used as a hypothetical example to illustrate the differences between classical and quantum systems. In classical systems, for example a ball trapped inside a heavy box, the particle can move at any speed within the box and it is no more likely to be found at one position than another. However, when the well becomes very narrow (on the scale of a few nanometers), quantum effects become important. The particle may only occupy certain positive energy levels. Likewise, it

can never have zero energy, meaning that the particle can never "sit still". Additionally, it is more likely to be found at certain positions than at others, depending on its energy level. The particle may never be detected at certain positions, known as spatial nodes. The particle in a box model provides one of the very few problems in quantum mechanics which can be solved analytically, without approximations. This means that the observable properties of the particle (such as its energy and position) are related to the mass of the particle and the width of the well by simple mathematical expressions. Due to its simplicity, the model allows insight into quantum effects without the need for complicated mathematics. It is one of the first quantum mechanics problems taught in undergraduate physics courses, and it is commonly used as an approximation for more complicated quantum systems. Mathematically we can write:

We have three distinct regions, because the potential energy function (potential for short) changes discontinuously. So, we have to solve the Schrödinger Equation three times. Fortunately, for Within the well, and , the solutions are trivial: , since . , so the particle is “free.”

The general solution is determined by the boundary conditions on the That is, we expect that At Then At .

. The parameters A, B, and and by the normalization requirement.

are

The choices of A=0 also solution but in that case

is not a valid solution.

From this we obtain the discrete allowed energy levels for the particle confined in the well.

The n is known as the principle quantum number. It labels the energy levels, or energy states of the particle. In other from classical physics we have obtained discrete energy values instead of continuous energy. Properties of wave function A wave function a) Single valued. A single-valued function is function that, for each point in the domain, has a unique value in the range. It is therefore one-to-one or many-to-one. At every point in space have only one value associated with it (single valued). If a wave function was not single valued, it would have multiple values for the same position, thereby ruining the probabilistic interpretation of the wave function. b) Continuous The function has finite value at any point in the given space. Otherwise it implies that particle does not exist at some points in the corresponding space. c) Differentiable Derivative of wave function is related to the flow of the particles. Therefore particle flow in the corresponding space should be continuous. d) Square integrable e) The wave function contains information about where the particle is located, its square being probability density. Therefore must be

Where

.

is conjugate of the wave function.

Example The wave function of a particle in the infinite well is obtained and defined . Is it valid wave function? Solution: The function is single valued, continuous, differentiable and square integrable if the constant A is finite. Therefore the function is a valid wave function. Example. Let two functions and cannot be a wavefunction but Solution Both functions are continuous and defined on the interval of interest. They are both single valued and differentiable. However, consider the integral of x: be defined for . Explain why could be a valid wavefunction.

is not square integrable over this range it cannot be a valid wavefunction. The Probability Interpretation of the Wavefunction At time , the probability of finding the particle within the interval and the square of the wavefunction. Calling this probability , we write: is given by

in Cartesian coordinates. The probability of finding the particle then becomes the probability of locating it within a volume : For the time being we will focus on one-dimensional situations. In most cases of interest, the potential is a function of position only, and so we can write:

The Schrödinger equation has two important properties. These are: 1. The equation is linear and homogeneous 2. The equation is first order with respect to time—meaning that the state of a system at some initial time determines its behavior for all future times. The Probability Interpretation and Normalization The probability interpretation tells us that gives the probability for finding the particle between and . To find the probability that a particle is located within a given region, we integrate. Square of absolute value of wave function Definition: Finding the Probability a Particle is Located in the Region The probability that a particle is located within is:

It is common to denote a probability density Probabilities Must Sum to 1

as

The total probability for any distribution must sum to unity. If the probability distribution is discrete with individual probabilities , this means that:

For a continuous probability distribution sum to unity means that:

, the fact that probabilities must

In quantum mechanics, this condition means that the particle is located somewhere in space with certainty

As we saw in the solution to the square well, a wavefunction that solves the Schrödinger equation is determined up to an unknown constant. In that case, the constant is called the normalization constant and we find the value of that constant by normalizing the wavefunction. Definition: Normalizing the Wavefunction When a wavefunction that solves the Schrödinger equation is multiplied by an undetermined constant , we normalize the wavefunction to find . Let us turn our attention to the particle in the infinite well problem. After applying boundary condition our function took the form:

The constant A can be determined from the normalization (Since sum of the probalities must be 1):
a 2 0
a

dx 1

A sin 2 kxdx 1
0

2

A2
A

a 2

1
2 a

Our solution is

n

x

2 n sin x for the particle inside the well. a a

Figure shows plot of the eigenvalues and wave function:

15

10

5

0 0.0 0.2 0.4 0.6 0.8 1.0

Example. Determine the probability that the particle in the infinite well is found in the intervals: , Solution The probability that a particle is located within is: , , .

Then

respectively.

Conservation of probability and probability current A continuity equation in physics is a differential equation that describes the transport of some kind of conserved quantity. Since mass, energy, momentum, electric charge and other natural quantities are conserved, a vast variety of physics may be described with continuity equations. Continuity equations are the (stronger) local form of conservation laws. All the examples of continuity equations below express the same idea, which is roughly that: the total amount (of the conserved quantity) inside any region can only change by the amount that passes in or out of the region through the boundary. A conserved quantity cannot increase or decrease, it can only move from place to place. In quantum mechanics, the probability current (sometimes called probability flux) is a concept describing the flow of probability density. In particular, if one pictures the probability density as an inhomogeneous fluid, then the probability current is the rate of flow of this fluid (the density times the velocity). The continuity equation is derived from the definition of probability current and the basic principles of quantum mechanics. The probability is given by:

And it is the probability that a measurement of the particle's position. The time derivative of this is

where the last equality follows from the product rule this further consider the time dependent Schrödinger equation

. In order to simplify

Or

Eliminating

and

we obtain

Comparing to the continuity equation we define:

is called probability current density. Then the continuity equation for probability:

In three dimensions (3D) it can be generalised as:

Or

Superposition of wave functions Quantum superposition refers to the quantum mechanical property of a particle to occupy all of its possible quantum states simultaneously. Due to this property, to completely describe a particle one must include a description of every possible state and the probability of the particle being in that state.] Since the Schrödinger equation is linear, a solution that takes into account all possible states will be a Linear combination of the solutions for each individual state. This mathematical property of linear equations is known as the superposition principle. Consider the superposition of stationary states which are solutions of the Schrödinger equation for a given potential V . Since these are stationary states, they can be written as:

At time t = 0, any wavefunction states: Time evaluation of this state is

can be written as a linear combination of these

Where

. and is defined by:

Inner product and probability The inner product of two wave functions

The particle can not be found in two state at the same time, then the product of basis states:

This property is known as the orthogonality of the wave functions. If we have normalized basis functions then they are orthonormal, which means that:

Since product of wave function gives probability of finding of particle in the given interval, the probability can be written as: Where .

The fact that basis states are orthogonal allows us to calculate the expansion coefficients using inner products. Calculating a Coefficient of Expansion The coeeficients of superposition of the wave functions can be calculated by using orthonormality and orthogonality properties of them. It is obvious that

Example. A particle of mass wavefunction is known to be:

is in a one-dimensional quantum well of width

The

Calculate If the energy is measured, what are the possible results and what is the probability of obtaining each result? What is the most probable energy for this state? Solution We begin by recalling that the th excited state of a particle in a one-dimensional

box is described by the wavefunction:

With the energy

Then we can write the superposition of the wave functions:

Using normalization

Therefore the wave function takes the form

The probablities and energies can be tabulated as: State number probability energy 1

2

3

Physical quantities: Observables and their operators In this lecture we study the relation between dynamical variables in classical and quantum mechanics and show that in the new quantum formalism these must be represented by operators acting on the wave function. We introduce the concept of commutator and derive the fundamental commutation relations holding for the position and momentum operators. Let’s start from the beginning. Physical quantities are things corresponding to aspects of the reality of a system that can be measured, that is, they can be characterized by numbers. In classical physics, considering a particle, the result of the measurement of a quantity A is a number a and this single number at time t. In quantum mechanics, what we said concerning position and momentum holds for any physical quantity. There is some probability law for the quantity. Consequently, the complete

result of a measurement of a quantity A on the state ψ is the whole set of issues associated probabilities . Position and momentum operators The classical view

and

Examples of dynamical variables (or observables ) in classical physics are the position x, the momentum p, the energy and the angular momentum . According to the classical view a particle has always univocally defined values for all possible observables at any time . They define indeed the state of the particle and evolve according to a deterministic equation (Newton equation). Moreover any classical observable can vary in a continuous way. The quantum view We know that in the microscopic world the position of a particle is known only in probabilistic terms. The outcome of a single measurement is random and we can only foresee an average value resulting from many identical experiments. The probability density for a position measurement can be calculated as follows: After a large number of measurements, will performed then we will have a collection of results whose mean value is can be related to probability :

This is called as well expectation value of the position. Note that this is not the most probable 2 value of x. That occurs where is a maximum. The variance of the measurements of x is
2

x2

x

2

.

Obviously we now know how to calculate the expectation value for any dynamical variable that depends on position alone. We have

But what about now if we want to know the expectation value of the momentum

? This is a

dynamical variable on its own and doesn’t depend upon x so that an integral such as the one above cannot hold in this case. To learn how to do this we remember that the new quantum theory we are studying must not contradict the old classical theory in the situations where the latter can be successfully applied. In other words quantum theory must include Newton theory as a special case holding within the appropriate limits. In Newton theory position and momentum are related by

We thus expect the new quantum theory to be such that

The fact that Newton equation holds, at least in an average sense, constraints the mathematical form of the momentum in the new quantum formalism. To obtain expectation value of momentum let us calculate:

We have shown before(see probability current density)

After some tedious calculations we can show that

Then momentum operator can be expressed as

Therefore we can obtain an operator for a physicsl observables of the quantum physics. As an example the kinetic energy operator can be obtained as follows:

As expected. In general in wave mechanics all dynamical variables are represented by operators that act on the wave function. The discussion above was in 1D but the generalization to 3D is straightforward. We note that in quantum mechanics all observables are represented by a suitable operator. Operator Algebra and Eigenvalue equations We must be careful when replacing the classical and with operator x and p since the order in which they appear is important. This is because two given operators A and B do not in general commute. Classical variables always commute, that is Operators, similar to the matrices and they may not commute: We can define the commutator (or commutation relation) If we say that A and B commute this physical means that the observables A and B can be measured simultaneously, there is no uncertanity relation between them. Example: Find the commutators of the momentum and position operator .

Solution The commutator can be written as

Important!!!! The first term can be evaluated as follows:

We have used derivative of product of two function. Then

Therefore the commutator can be written as

!Remember uncertainity relation Eigenvalue Equation The operators act on a function. The eigenvalue equation can be written as: Where O is operator, Solution We can write the eigenvalue equation is eigenvector and a is eigenvalue.

Example: Determine the eigenfunction of the momentum operator

Where p is eigenvalues of the momentum operator. We solve the equation and we obtain

Operators whose expectations are real Solution Lets check if

are called Hermitian operators.

Example: Check weather the momentum operator is hermitian or not?

The integral is evaluated at hermitian.

and

, where

vanishes therefore momentum operator is

Hermitian operators also gives real eigenvalues.

*This lecture notes collected from the references given below http://galileo.phys.virginia.edu/ http://en.wikipedia.org/wiki/Particle_in_a_box An introduction to Quantum Mechanics COURSE NOTES by: Paolo BONIFACIO Quantum Mechanics Demystified (Mcgraw-HILL) DAVID McMahon

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