Course Title : Quantum Chemistry and Spectroscopy Lecturer : Dr.

Bakhtyar Kamal Aziz Chemistry Department / College of Science Contact Detail : Tel. 07701902821 Course overview : Classical mechanics was invented by Sir Isaac Newton to describe and predict the motions of objects such as the planets as they move about the sun. Although classical mechanics was a great success when applied to objects much larger than atoms, it was a complete failure when applied to atoms and molecules. It was superseded by quantum mechanics, which has enjoyed great success in explaining and predicting atomic and molecular properties. However, quantum mechanics was built upon classical mechanics, and someone has said that if classical mechanics had not been discovered prior to quantum mechanics, it would have had to be invented in order to construct quantum mechanics. Sir Isaac Newton, 16421727, was a great British mathematician and physicist who was also one of the inventors of calculus. There are some important differences between classical mechanics and quantum mechanics. Classical mechanics, like thermodynamics, is based on experimentally grounded laws, while quantum mechanics is based on postulates, which means unproved assumptions that can be accepted only if their consequences agree with experiments. However, thermodynamics, classical mechanics, and quantum mechanics are all mathematical theories. Galileo once wrote The book of nature is written in the language of mathematics. We will review some of the mathematics that we use as we encounter it, and there are a few mathematics topics presented in the appendixes. There are also several books that cover the application of mathematics to physical chemistry. Email: bakhtyar.aziz@univsul.net

Course Objectives:
The main objectives of the course are to understand these points: 1. The molecular nature of matter is studied through quantum mechanics. 2. Classical mechanics is the historical precursor of quantum mechanics. In this theory the state of a system is specified by giving values of coordinates and velocities. 3. Classical mechanics accurately describes the motions of objects of large mass that are moving at speeds much slower than the speed of light. 4. Classical mechanics ascribes exact trajectories to particles. 5. The classical wave equation describes the vibrations of strings and light waves. 6. The old quantum theory includes Plancks black-body radiation theory, Einsteins theory of the photoelectric effect, and Bohrs theory of the hydrogen atom. 7. The old quantum theories contained quantization as hypotheses. 8. The old quantum theories have been superseded by quantum mechanics.

Course Reading list and References: 12345Physical Chemistry, 3rd edition , Robert G. Mortimer, 2008 Elsevier. Essentials Physical Chemistry, S. Chand Quantum Chemistry, 3rd edition, John P. Lewe and Kirk A. Petreson, 2006. Quantum mechanics in Chemistry, Melvin W.Hanna Quantum mechanics, Powell & Crasemann.

A/ Mathematical Preliminaries 1-Coordinate Systems. 2-Determinats. 3-Sammation & Products Notation. 4-Vectors. 5-Complex numbers. 6-Operators. 7-Eigen Value Equations.

B/Classical Mechanics 1-Conservative Systems. 2-Example of Newtonian Mechanics. 3-Lagrangian & Hamiltonian Forms of the equation of Motion. 4-Basic assumptions of Classical Mechanics.

C/Quantum Mechanics The origins of quantum mechanics. *The Failurs of classical Mechanics. 1-Black body Radiation. 3-Heat Capacities. 4-Atomic & Molecular Spectra *Wave Particle Duality. *Wave Particle Duality.

1-The Particle character of EMR. 2-The Wave character of particles.

D/The Dynamics of Microscopic Systems. 1-Schrodinger Equation. 2-Born interpretation of Wavefunction.

E/Quantum Mechanical principles. 1-The Information in a Wavefunction. 2-The uncertainty principle.

F/Applications of Quantum Theory.

A/Mathematical Preliminaries
1-Coordinate Systems. The purpose of a coordinate system is to describe a point, a curve, or a surface in space. The choice of the kind of the coordinate is depend on the type of the problem. i/Cartesian Coordinates: Is the most familiar. A point (P) in Cartesian space is represented by the axes X , Y , and Z . (the distance on each axis).
Z

P z

O x

ii/Spherical Polar Coordinates:A point P(r , , ) is represented by one distance (r) and two angles ( , ) r :-is the length of the line between the origin and the point (P). :-The angle (polar angle) is the angle between Z -axis and the line (OP) :-Is called the Azimuthal angle and it is angle between X-axis and projection of line (OP) in the XY plane.

r
O Y

Cartesian coordinates are related to the spherical polar coordinates by the relations:X= r sin cos Y= r sin sin Z= r cos

iii/Cylinderical Coordinates :The location of a point (P) is given by two distances and one angle. The two distances are (Z) and the length of the projection of line (OP) in the plane XY , (p). The angle is the azimuthal angle between X-axis and the projection of OP in the plane XY.
Z

P (p, , z)

O p

The relations are given by :X= cos Y= sin Z=z

iv/ Confocal ellipsoidal coordinates :This is used for problems involving two centers, A and B ,affixed distance R apart. The lines AP and BP define a plane, the line formed by the intersection of this plane with XY Plane defines the angle . The point P ( , , ) can be defined by specifying the distances rA and rB along lines AP and BP , respectively , and the angle . Elliptical coordinates and are then defined as:-

The third coordinate is the angle described above .

-1 -1

In problems of quantum mechanics, one will require to evaluate integrals over all space. To do this, the differential volume element, called ( d ) , must be known for each kind of coordinate system. These volume elements for the various coordinate systems, and the limits of integration that include all space, are :Cartesian d = dx dy dz - x+ - y+ - z+ Spherical polar

d = r2 Sin dr d d

0r+ 0 0 2

Cylinderical

0p+ 0 2 - z +

Elliptical 1

-1 +1 02

2\ Determinants There are many physical problems of interest that are most conveniently described by writing down array of mathematical quantities. Two types of arrays are used in quantum chemistry: Determinants and matrices. A determinant is any arrangement of N2 quantities in to a square array with N rows and N columns. The number N of rows and columns is called the order of the determinant. Thus the arrays XE B 8 5 3 3 5 8 5 3 8 order = 3

Are determinants

B X-E order = 2

Each element in the array will have two subscripts. The first define the row the second define the column in which the element appears. So the quantity aij is the element from i th row and j th column of The most convenient way to evaluate a determinant is to make use of the method of ( signed minors ) or ( cofactors ) . The minor of an element Aij is the ( N 1 ) th order determinant remaining when the row i and column j of the original determinant are struck out . To form the cofactor, the minor is given a sing according to the position of the element Aij in the original determinant . The sing is ( - 1 ) i+j

A determinant is evaluated by picking either a row or a column, forming the product of each element in the row (or column) with its cofactor, and summing the products, (+ve, -ve, +ve, -ve etc).

Example : Evaluate the determinant below by the method of cofactors. 8 3 5 5 5 3 3 8 8 5 = 8 3 8 8 - 5 5 8 3 8 + 3 5 3 3 5

= 8 ( 40-24) 5(24-40) + 3 ( 9 25) = 160

Properties of determinants: 1- The value of the determinant changes sign when two rows or two columns are interchanged. 2- If two rows or two columns are identical, the determinant is equal to zero . Example 2 : Evaluate the determinant below by the method of cofactors . 4 1 2 3 2 =4 3 4 1 2 2 3 3 4 4 1 3 4 1 3 4 1 2 4 1 2 1 2 3 3 4 4 1 1 2 1 2 4 1 2 2 3 1 -- 3 2 3 3 4 2 3 4 3 4 1

- 1

+2

= 4 X ( 16 64 ) 1 X ( 8 48 ) + 2 X ( 6 36 ) 3 X ( 3 27 ) = - 140

3/ Summation and Product Notation In physical chemistry, we often see equations of the of the form :y = a1 + a2 + a3 ai + .. an.. (1) Z = a1a2 ai . am ...(2)

To simplify , is used with limits of summation placed below and above the . A similar is used for multiplication.

Equation (1) can written

And equation (2) as

Example :- Let ai be the series of even integers starting with a1=2. Evaluate

Y= (2+4+6+8) = 20 Z = (2 X 4 X 6 X 8 ) =384

4/ Vectors A vector is used to represent a physical quantity which has both magnitude and direction ( force , magnetic field or acceleration ). A vector can be represented by a symbol with an arrow above or below it ( It can be represented by boldface type letter also.
Z

or

).

r : is a radius vector
r : is the magnitude op : is the direction .

Any vector can be written in terms of its components ( projections )along the three axis. To do this , three mutually perpendicular unit vectors called i , j , k are defined that point along the x , y , z axes respectively . Then any vector can be written in term of its components .

r = xi + yj + zk

The combination of vectors follow some rules :1-Addition :- addition of vectors can be done either graphically or analytically. A+B = C Vector addition is commutative , X+Y = Y+X

And associative , (X + Y) + Z = X + (Y + Z ) = X + Y + Z 2- Subtraction :- vectors are subtracted by adding the negative of the appropriate vector.
A C +B D A Sustraction Addition A+B=C A-B=D -B

3-Magnitude By elementary trigonometry.

Z

X2 + Y2 + Z2 = r2

r = (X2 + Y2 + Z 2 )1/2

4-Multiplication :A.B is called dot or scalar product. AxB is called cross or vector product. A.B = AB cos ( 180 )

If two vector are perpendicular cos = cos 90 = 0 So A.B = 0 The two vector are said to be orthogonal. A.B = AxBx + AyBy + A2B2 The cross product AxB is defined as :AxB = n AB sin n :- is a unit vector perpendicular to both A and B .

If A and B are parallel , sin = sin 0 = 0 AxB = 0 . The right-hand rule must be used in evaluating the cross product. To use this rule , place the bottom edge of the right palm along A and curl the fingers toward B . The thumb will then point in the direction of ( n ) . As a result of the this rule :AxB BxA In fact AxB = - BxA ( Not cumulative ).

The geometrical interpretation of the cross product AxB is that of a vector perpendicular to both A and B whose length is equal to the area of the parallelogram defined by A and B . AxB is most conveniently written in the form of a determinant. AxB = i j k Ax Ay Az Bx By Bz

= i(AyBz - AzBy) j(AxBz AzBx) + k(AxBy AyBx)

B sin

Division of vectors is not defined. Differentiation of vectors is done simply by differentiating its components.

r = xi + yj + zk

5/ Complex Numbers A complex number is one which contain ( A + iB If is a complex number ) ( i ) as it is usually symbolized .

C = A + iB

then the complex conjugate of C , called C* is formed by replacing ( i) wherever it appears by ( -i) C* = A iB The magnitude or absolute value of a complex number is defined as : (CC*)1/2 = (A2 + B2)1/2 The magnitude of a complex number is always real. Addition and subtraction follow the same rules as for vectors, that is the real and imaginary parts are added independently. Thus if Z1 =X1 + iy1 Z2 = X2 + iy2 Then Z1+Z2 = (X1 + X2) + i(y1 + y2 ) .

Eulers, formula

eix = cos x + i sin x

Examples:Quantities in the form A +iB a) (1 + i)3 b) (x+iy) (4 + iv) c) ei/2

(1+i)3 = (1+i) (1+i)2 = (1+i) (1+2i-1) =2i+2i2 = 2i-2

6-Operators An operator is a symbol that tell us to do something to what follows the symbol . For , is an operator telling us to take the square root of what follows (2).

d/dx (x2+5x+1) d/dx is an operator . General operator are indicated by a symbol with a caret over it , P or Q . If P = (

Q =(

Then

PQ =

Operators are not necessarily commutative, because operations are like vector multiplications so, when dealing with operators, one must be careful of the order of operation sequence.
PQ
=

QP

since

An operator that will be used frequently in quantum mechanics is :This operator is related to the kinetic energy. In Cartesian coordinates it can be seen

The

, wher (f) is scalar function , is called the gradient of (f) .

Ex:- if f = x2 + y2 + z2 then f = 2xi + 2yi + 2zk In Quantum mechanics , only linear operators are used . An operator is linear if it is true that P (F+g) = Pf + P g
Or

Paf = a P f

e.g :

7-Eigenvalue Equations An equation of type :-

P (qi) G(qi) = p G(qi)

P(qi) is an operator G(qi) is a function p is a constant called eigenvalue equation
P and p is eigenvalue.

both involving variable qi

In Quantum mechanics , P is generally a differential operator , therefore the eigenvalue equation is a differential equation . The principal mathematical problem of quantum mechanics is to find the solution G and the eigenvalues p to these eigenvalue equations.

Ex:-Let us choose G(x) = sin ax If we differentiate twice , it result in the same original function :G (x) = d2/dx G(x) = d/dx ( d/dx sin ax ) = d/dx ( a cos ax ) = -a2 sin ax If a :- constant Then the function G(x) = sin ax is an eigenfuction of the operator d/dx2 and the eigenvalue is (-a2) .

G(x) =A e-ax G(x) = d/dx (d/dx A e ax ) = d/dx (- A a e- ax) = A.a2 e- ax a2 = eigenvalue . show that eax2 is not eigenfunction of d/dx =d/dx = eax2

= d/dx eax2 = 2axeax2

=2ax Not eigenfunction because x is variable.

Classical Mechanics
Mechanics deal with the motion of bodies and with forces affect these motions. Before 1900, it was a powerful example of mathematical theories to predict, correlate and interpret observations on the nature of the physical world. Classical mechanics was first based on Newtons laws of motion. More powerful formulations were made by Lagrange and Hamilton. Quantum mechanics needs to have some knowledge about classical mechanics, the problem is to solve the differential equations resulting from Newtons 2 nd law, were:: the force acting on (i)th particle in the system ai : its acceleration

The construction of operators Operators for other observables of interest can be constructed from the operators for position and momentum. For example, the kinetic energy operator T can be constructed by noting that kinetic energy is related to linear momentum by T=p2/2m where m is the mass of the particle. It follows that in one dimension and in the position representation

In three dimensions the operator in the position representation is

The operator 2, which is read 'del squared' and called the laplacian, is the sum of the three second derivatives. The potential energy of a particle in one dimension, V(x), becomes multiplication by the function V{x) in the position representation. The same is true of the potential energy operator in three dimensions. For example, in the position representation the operator for the Coulomb potential energy of an electron in the field of a nucleus of atomic number Z is the multiplicative operator

where r is the distance from the nucleus to the electron. It is usual to omit the multiplication sign from multiplicative operators, but it should not be forgotten that such expressions are multiplications. The operator for the total energy of a system is called the hamiltonian operator and is denoted H: H=T+V The name commemorates W.R. Hamilton's contribution to the formulation of classical mechanics. To write the explicit form of this operator we simply substitute the appropriate expressions for the kinetic and potential energy operators in the chosen representation. For example, the hamiltonian for a particle of mass m able to move in one dimension is

where V(x) is the operator for the potential energy. Similarly, the Hamiltonian operator for an electron of mass me in a hydrogen atom is

The general prescription for constructing operators in the position representation should be clear from these examples. In short: 1. Write the classical expression for the observable in terms of position coordinates and the linear momentum. 2. Replace x by multiplication by x, and replace px by ( /i) / x (and likewise for the other coordinates).

Conservative systems
Is a system in which the sum of the kinetic and potential energy remains constant with time ( isolated system), and it can not have internal dissipative forces such as friction. T+V=E Conservative system represent mathematically the potential function V , that is := ----------------------------------(1) ( -ve) gradient of some

From Newtons 2nd law:-

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

If eq. 1 holds :

Substitution of eq. 3 into 2 gives:

E will represent total energy of a particle ( E ). So T+V=E

An example on Newtonians mechanics ( Classical Oscillator )

A simple realization of the harmonic oscillator in classical mechanics is a particle which is acted upon by a restoring force proportional to its displacement from its equilibrium position. Considering motion in one dimension, this means F=-kx ..(1)

Such a force might originate from a spring which obeys Hooke's law, as shown in Fig. 1. According to Hooke's law, which applies to real springs for sufficiently small displacements, the restoring force is proportional to the displacement either stretching or compression from the equilibrium position. The force constant k is a measure of the stiffness of the spring.

The variable x is chosen equal to zero at the equilibrium position, positive for stretching, negative for compression. The negative sign in (1) reflects the fact that F is a restoring force, always in the opposite sense to the displacement x.

Applying Newton's second law to the force from Eq (1), we find

where m is the mass of the body attached to the spring, which is itself assumed massless. This leads to a differential equation of familiar form, although with different variables: The dot notation (introduced by Newton himself) is used in place of primes when the independent variable is time. The general solution to (3) is

which represents periodic motion with a sinusoidal time dependence. This is known as simple harmonic motion and the corresponding system is known as a harmonic oscillator. The oscillation occurs with a constant angular frequency

This is called the natural frequency of the oscillator. The corresponding circular frequency in hertz (cycles per second) is

The general relation between force and potential energy in a conservative system in one dimension is

Thus the potential energy of a harmonic oscillator is given by

which has the shape of a parabola, as drawn in Fig. 2. A simple computation shows that the oscillator moves between positive and negative turning points xmax where the total energy E equals the potential energy 1/2kx2max while the kinetic energy is momentarily zero. In contrast, when the oscillator moves past x = 0, the kinetic energy reaches its maximum value while the potential energy equals zero.

Lagrang and Hamilton forms of the equations of motion

For problems of equations of motion in other coordinate system (except Cartesian), it is difficult to write down the equations of motion. So, it is more convenient to derive equations of motion in the form which is independent of a coordinate system. Such equations were derived by two Mathematician Lagrang and Hamilton. Hamiltonian form is more important because it is used in the transformation of classical to quantum mechanics, it is necessary to introduce general coordinates, velocities and momenta. Suppose a conservative system containing three particles. Inorder to specify completely the state of the system at a given time (t), we have to specify the position and velocities of the three particles. To do this, we have to specify nine (x1, y1, z1, x3, y3, z3) and nine velocities ( . In general, for a system with N particles, we have to specify 3N coordinates and 3N velocities. Such system would have 6N degrees of freedom. To formulate classical mechanics in a general way, we introduce for a system containing N particles, 3N generalized coordinates (qi), and 3N generalized velocities Then we derive the Lagrangian and Hamiltonian forms of the equations of motion in terms of these generalized coordinates and velocities. The generalized quantities are given a specific form. The Lagrangian function L( is defined as :-

( T ) is the kinetic energy in terms of generalized velocities & coordinates and time (t), V is the potential energy in terms of generalized coordinate and the time (t). The Lagrangian fuction (L) (for conservative system) and potential energy (V) will not explicitly depend on the time.

Basic assumption of classical mechanics

It was implied that an experimentalist can precisely measure the positions and the velocities of all particles in a system at the same time (t) inorder to describe the state of the system. When the initial state is defined, the laws of mechanics and knowledge of the forces acting on the system enable the system to be characterized at any later time. This means, an experimentalist can measure the position, velocity, energy, momentum,etc for any particle at any time and compare it with the theoretical prediction. The three statements summarize the assumption inherent in this view:1- There is no limit to the accuracy with which one or more of the dynamical variables of classical system can be simultaneously measured except the limit imposed by the precision of the measuring instrument. 2- There is no restriction on the number of dynamical variables that can be accurately measured simultaneously. 3- Since the expressions for velocity are continuously varying functions of time, the velocity, and hence the kinetic energy, can vary continuously, that is, there is no restrictions on the values that a dynamical variable can have.

Quantum Mechanics
Origins of Quantum Mechanics It was thought that the motion of atoms and subatomic particles could be expressed using the laws of classical mechanics which was introduced by Isaac Newton. These laws were very successful at explaining the motion of everyday objects and planets. Classical Mechanic principles allow:1- The prediction of precise trajectory for particles. 2- Allow translational, Vibrational and rotational modes of motion to be exited to any energy simply by controlling the applied energy. The failures of Classical Mechanics

1- Black-body radiation
In retrospectand as will become clearwe can now see that theoretical physics hovered on the edge of formulating a quantum mechanical description of matter as it was developed during the nineteenth century. However, it was a series of experimental observations that motivated the revolution. Of these observations, the most important historically was the study of black-body radiation, the radiation in thermal equilibrium with a body that absorbs and emits without favouring particular frequencies. A pin-hole in an otherwise sealed container is a good approximation (Fig. 0.1). Two characteristics of the radiation had been identified by the end of the century and summarized in two laws. According to the Stefan-Boltzmann law, the excitance, M, the power emitted divided by the area of the emitting region, is proportional to the fourth power of the temperature:

The Stefan-Boltzmann constant, a, is independent of the material from which the body is composed, and its modern value is 5.67x10 -8 Wm-2K-4. So, a region of area 1 cm2 of a black body at 1000 radiates about 6 W if all fre -frequencies are taken into account. Not all frequencies (or wavelengths, with = c/v), though, are equally represented in the radiation, and the observed peak moves to shorter wave-lengths as the temperature is raised. According to Wien's displacement law, mT = Constant -------------(2) with the constant equal to 2.9 mm K.

One of the most challenging problems in physics at the end of the nineteenth century was to explain these two laws. Lord Rayleigh, with minor help from James Jeans,1 brought his formidable experience of classical physics to bear on the problem, and formulated the theoretical Rayleigh-Jeans law for the energy density (, the energy divided by the volume) in the wavelength range d:

where is Boltzmann's constant (k = 1.381 x 10 -23JK-1). This formula sumsummarizes the failure of classical physics. It suggests that regardless of the temperature, there should be an infinite energy density at very short wavewavelengths. This absurd result was termed the ultraviolet catastrophe by Ehrenfest. At this point, Planck made his historic contribution. His suggestion was equivalent to proposing that an oscillation of the electromagnetic field of fre- frequency v could be excited only in steps of energy of magnitude hv, where h is a new fundamental constant of nature now known as the Planck constant. According to this quantization of energy, the oscillator can have the energies 0, hv, 2hv,... and no other energy. Classical physics allowed a continuous variation in energy, so even a very high frequency oscillator could be excited with a very small energy: that was the root of the ultraviolet catastrophe. Quantum theory is characterized by discreteness in energies (and, as we shall see, of other properties), and the need for a minimum excitation energy effeceffectively switches off oscillators of very high frequency, and hence eliminates the ultraviolet catastrophe. When Planck implemented his suggestion, he derived the following Planck distribution for the energy density of a black-body radiator:

This expression, which is plotted in Fig. 0.2, avoids the ultraviolet catastrophe, and fits the observed energy distribution extraordinarily well if we take h =6.626 x10 -34 Js. Just as the Rayleigh-Jeans law epitomizes the failure of classical physics, the Planck distribution epitomizes the inception of quantum theory. It began the new century as well as a new era, for it was pub-published in 1900.

Fig. 0.2 The Planck distribution.

2- Heat capacities
In 1819, science had a deceptive simplicity. Dulong and Petit, for example, were able to propose their law that 'the atoms of all simple bodies have exactly the same heat capacity'. In modern terms, we would phrase the law in terms of the molar isochoric (constant volume) heat capacity, CV,m, and write Cv,m 3R for a solid element, where R is the gas constant (R = NAk, with NA the Avogadro constant). Dulong and Petit's rather primitive observations, though, were done at room temperature, and it was unfortunate for them and for classical physics when measurements were extended to lower temperatures. It was found that all elements had heat capacities lower than predicted by Dulong and Petit's law, and the values tended toward zero as T 0. Dulong and Petit's law was easy to explain in terms of classical physics. All it was necessary to do was to suppose that each atom acted as an oscillator in three dimensions, and then to use classical physics to calculate the corresponding heat capacity. That the heat capacities were smaller than predicted was a serious embarrassment. Einstein recognized the similarity between this problem and blackbody radiation, for if each atomic oscillator required a certain minimum energy before it would actively oscillate and hence contribute to the heat capacity, then at low temperatures some would be inactive and the heat capacity would be smaller than expected. He applied Planck's suggestion for electromagnetic oscillators to the material, atomic oscillators of the solid, and deduced the following expression:

where the Einstein temperature, E, is related to the frequency of atomic oscillators by E = /k. This function is plotted in Fig. 0.3, and closely reproduces the experimental curve. In fact, the fit is not particularly good at very low temperatures, but that can be traced to Einstein's assumption that all the atoms oscillated with the same frequency. When this restriction was removed by Debye, he obtained

where the Debye temperature, D, is related to the maximum frequency of the oscillations that can be supported by the solid. This expression gives a very good fit with observation.

The importance of Einstein's contribution is that it complemented Planck's. Planck had shown that the energy of radiation is quantized; Einstein showed that matter is quantized too. Quantization appears to be universal. Neither was able to justify the form that quantization took (with oscillators excitable in steps of ), but that is a problem we shall solve later in the text.

3- The photoelectric and Compton effects

Visible or ultraviolet radiation impinging on clean metal surfaces can cause electrons to be ejected from the metal. Such an effect is not inconsistent with classical theory since electromagnetic waves are known to carry energy and momentum. But the detailed behavior as a function of radiation frequency and intensity can not be explained classically. The energy required to eject an electron from a metal is determined by its work function . For example, sodium has = 1.82 eV. The electron-volt is a convenient unit of energy on the atomic scale: 1 eV = 1.602x10-19J. This corresponds to the energy which an electron picks up when accelerated across a potential difference of 1 volt. The classical expectation would be that radiation of sufficient intensity should cause ejection of electrons from a metal surface, with their kinetic energies increasing with the radiation intensity. Moreover, a time delay would be expected between the absorption of radiation and the ejection of electrons. The experimental facts are quite different. It is found that no electrons are ejected, no matter how high the radiation intensity, unless the radiation frequency exceeds some threshold value o for each metal. For sodium o=4.39x1014Hz (corresponding to a wavelength of 683 nm), as shown in Fig. 6. For frequencies () above the threshold, the ejected electrons acquire a kinetic energy given by

Threshold value

Evidently, the work function can be identified with ho, equal to 3.65x10-19J =1.82 eV for sodium. The kinetic energy increases linearly with frequency above the threshold but is independent of the radiation intensity. Increased intensity does, however, increase the number of photoelectrons. Einstein's explanation of the photoelectric effect in 1905 appears trivially simple once stated. He accepted Planck's hypothesis that a quantum of radiation carries an energy h. Thus, if an electron is bound in a metal with an energy , a quantum of energy ho = will be sufficient to dislodge it. And any excess energy h( - o) will appear as kinetic energy of the ejected electron. Einstein believed that the radiation field actually did consist of quantized particles, which he named photons. Although Planck himself never believed that quanta were real, Einstein's success with the photoelectric effect greatly advanced the concept of energy quantization.

The puzzling features of the effect were that the emission was instantaneous when the radiation was applied, however low its intensity, but there was no emission, whatever the intensity of the radiation, unless its frequency exceeded a threshold value typical of each element. It was also known that the kinetic energy of the ejected electrons varied linearly with the frequency of the incident radiation. Einstein pointed out that all the observations fell into place if the electromagnetic field was quantized, and that it consisted of bundles of energy of magnitude h. Einstein viewed the photoelectric effect as the outcome of a collision between an incoming projectile, a photon of energy h, and an electron buried in the metal. This picture accounts for the instantaneous character of the effect, because even

one photon can participate in one collision. It also accounted for the frequency threshold, because a minimum energy (which is normally denoted and called the 'work function' for the metal) must be supplied in a collision before photoejection can occur; hence, only radiation for which h > can be successful. When a potential is applied so as to stop the electron flow, the kinetic energy is just balanced by the potential energy of an electron in an electric field, thus:

e = electric charge

Plotting shown above.

should give a straight line of slop h/e and intercept

as

Example: What is the minimum energy that photons must possrss in order to produce photoelectric effect with platinum metal?? The threshold frequency for Pt is 1.3x1015sec-1. Solution: E= = (6.625 x 10-27 egr sec)(1.3x1015 sec-1)

= 8.6x10-12 erg

4- Atomic Spectra (Line Spectra)

Most of what is known about atomic (and molecular) structure and mechanics has been deduced from spectroscopy. Fig. 7 shows two different types of spectra. A continuous spectrum can be produced by an incandescent solid or gas at high pressure. Blackbody radiation, for example, is a continuum. An emission spectrum can be produced by a gas at low pressure excited by heat or by collisions with electrons. An absorption spectrum results when light from a continuous source passes through a cooler gas, consisting of a series of dark lines characteristic of the composition of the gas. Frauenhofer between 1814 and 1823 discovered nearly 600 dark lines in the solar spectrum viewed at high resolution. It is now understood that these lines are caused by absorption by the outer layers of the Sun.

Figure 7. Continuous spectrum and two types of line spectra Gases heated to incandescence were found by Bunsen, Kirkhoff and others to emit light with a series of sharp wavelengths. The emitted light analyzed by a spectrometer (or even a simple prism) appears as a multitude of narrow bands of color. These so called line spectra are characteristic of the atomic composition of the gas. The line spectra of several elements are shown in Fig. 8.

Figure 8. Emission spectra of several elements It is consistent with classical electromagnetic theory that motions of electrical charges within atoms can be associated with the absorption and emission of radiation. What is completely mysterious is how such radiation can occur for discrete frequencies, rather than as a continuum. The breakthrough that explained line spectra is credited to Neils Bohr in 1913. Building on the ideas of Planck and Einstein, Bohr postulated that the energy levels of atoms belong to a discrete set of values En, rather than a continuum as in classical mechanics. When an atom makes a downward energy transition from a higher energy level Em to a lower energy level En, it caused the emission of a photon of energy h = Em - En -------------------------(4)

This is what accounts for the discrete values of frequency in emission spectra of atoms. Absorption spectra are correspondingly associated with the annihilation of a photon of the same energy and concomitant excitation of the atom from E n to Em. Fig. 9 is a schematic representation of the processes of absorption and emission of photons by atoms. Absorption and emission processes occur at the same set frequencies, as is shown by the two line spectra in Fig. 7.

Figure 9. Origin of line spectra. Absorption of the photon shown in blue causes atomic transition from E0 to E2. Transition from E2 to E1 causes emission of the photon shown in red.

Rydberg (1890) found that all the lines of the atomic hydrogen spectrum could be fitted to a simple empirical formula

where R, known as the Rydberg constant, has the value 109,677 cm-1. This formula was found to be valid for hydrogen spectral lines in the infrared and ultraviolet regions, in addition to the four lines in the visible region. No analogously simple formula has been found for any atom other than hydrogen. Bohr proposed a model for the energy levels of a hydrogen atom which agreed with Rydberg's formula for radiative transition frequencies. Inspired by Rutherford's nuclear atom, Bohr suggested a planetary model for the hydrogen atom in which the electron goes around the proton in one of a set of allowed circular orbits, as shown in Fig 8. A more fundamental understanding of the discrete nature of orbits and energy levels had to await the discoveries of 192526, but Bohr's model provided an invaluable stepping-stone to the development of quantum mechanics.

Figure 8. Bohr model of the hydrogen atom showing three lowest-energy orbits.

Figure 9. A stylized representation of the Bohr model for a multielectron atom.

5- Structure of atoms Rutherford had proposed the nuclear model of the atom. In this model, the positive charge, and most of the mass, is concentrated in the center of the atom, called nucleus, electrons were postulated to revolve around it like planets around the sun. A simple consequence of Newtons law of motion that for an electron subject to the attractive force from the nucleus to move in a stable orbit, it must be accelerated. And according to the classical thermodynamics, an accelerated charge must continuously lose energy by radiating. The paradox in this view of the structure of atoms is that an atom should not be stable. That is, as the electrons radiate, it will lose energy and spiral inward till it collide with nucleus. But we see that atoms are stable, and they radiate only when they are execited. Bohr try to explain the differences between experimental and theoretical ideas. Bohrs hypothesis was that the lines in an atom spectrum come from a transition of an electron between two discrete states in an atom, and he made some assumptions: 1- The Plank-Einstein relation: transition between two energy levels is related to the frequency of spectral line. 2- In the discrete states, the magnitude of the angular momentum of the electron can only have the values L (angular momentum) = 3- The behavior of electron transition can not be explained classically. To calculate the allowed orbits by Bohr, we start with the 2nd law of Newton:-

The force is the columbic force between the ( +ve) nucleus and (-ve) electron:Z = nuclear charge

From the assumption of Bohr:

So the value of ( r ) is restricted to certain orbits, that is So the smallest allowed orbit in the hydrogen atom, Z=1 , n=1 = 0.529 Ao The total energy E= T + V

Since the system is conservative .

it mean only discrete energy levels appear because (n) is Integer value.

Bohrs theory was successful for hydrogen atom, but failed to account for the spectrum of any atom having more than one electron. More general equations were needed. Louis de Broglie when, in 1924, he suggested that any particle, not only photons, travelling with a linear momentum p should have (in some sense) a wavelength given by the de Broglie relation:

This idea was confirmed by the electron diffraction experiments made by Davisson &Germer. Diffraction is a property that is only associated with wave motion. .[Enistein]

and

r= distance between e- and nucleus N = principle quantum number Example: Estimate the wavelength of electrons that have been accelerated from rest through a potential difference of 1 kV.

p=mv or mc

The Debroglie wavelength is

= 3.88x10-11 m

The formulation of Quantum Mechanics It was studied in two different ways:1- Schrodinger wavefunction ( wave mechanics). 2- Heisenbeg matrix property ( matrix mechanism). In the more general treatments of quantum mechanics by Dirac & Neuman, showed that Schrodinger and Heisenberg approches are specific cases of a general theory.

The Postulates of Quantum Mechanics Postulate I :(a) is a wavefunction that contain all informations about the state of a dynamical system. It ( ) could be time dependent (if the observable properties do not change with time) and the system is said to be stationery state. (b) The quantity * d is proportional to the probability of finding ( q1) between ( q1 and q1+dq1) , q2 between q2 and q2+dq2 . * is a product of and its complex conjugate and it is called probability density. Properties of : 1- The fuction should be continous, and its 1st and 2nd derivative should be continous too. 2- It should be single valued. 3- It should have an integrable square. d = volume element = dx dy dz When the above equation is true, then the function is said to be normalized. ( 1 ) means 100% probability, in such case the is siad to be normalized.

Postulate II
For any observable property of a system, there exists a coresponding linear Hermitian operator, and the physical properties of the observable can be inffered from the mathematical properties of its associated operator. A Hermitian opeator is defined by the :-

Let us constract the quantum mechanical operator for the kinetic energy T. The classical form for a particle in cartisian coordinate is :-

The classical form for the total energy is Hamiltonian function, and the corresponding operator is called the Hamiltonian. For a single particle :
H= T+V
v v v

------- ( 2 )

Postulate III:Suppose that operator corresponding to an observable and there is a set of identical systems in state as is a number. is an eigenfunction of that is
v v v

Then if we make a series of experiments of the quantity corresponding to on different members of the set, we will always get the result ( as), ( like px, py and pz orbitals) ( different wave functions that give the same eigenvalue).

Substitute eq. 3 in 4

or

This is Schrodinger equation for a single particle in a stationary state.

Application of Postulates to Simple Systems

The free particle motion The three basic modes of motion-translation (motion through space), vibration, and rotation-all play an important role in chemistry because they are ways in which molecules store energy. Gas-phase molecules, for instance, undergo translational motion and their kinetic energy is a contribution to the total internal energy of a sample. Molecules can also store energy as rotational kinetic energy and transitions between their rotational energy states can be observed spectroscopically. Energy is also stored as molecular vibration and transitions between vibrational states are responsible for the appearance of infrared and Raman spectra. Consider a particle in a box, in which a particle of mass (m) is confined between two walls at x = 0 and x = L: the potential energy (V) is zero inside the box but rises abruptly to infinity at the walls. This model is an idealization of the potential energy of a gas-phase molecule that is free to move in a one-dimensional container. However, it is also the basis of the treatment of the electronic structure of metals and of a primitive treatment of conjugated molecules. The particle in a box is also used in statistical thermodynamics in assessing the contribution of the translational motion of molecules to their thermodynamic properties.

Etot = Ekin Shrodinger eq. for one dimensional system. V= zero ( zero pot. Energy inside the box)

The solution for he above equation is :-

side of the box. x: distance along the x-axis A: amplitude of wave

n=1,2,3 .. eigenvalue The particle in a box assumes its lowest possible energy when n = 1, namely

To complete the calculation of the wavefunctions, they should be normalized, this requires that :-

When the equation is evaluated, ( A ) must have the value A= So, the allowed wavefunctions and energies for the particle in a box are:-

On x-axis On y-axis On z-axis

If nx = ny = nz = 1

And ax = ay = az = a
= (

If nx =2 So

n y = nz = 1 (4+1+1)= = 6 x 27.8 x

If nx = nz = 1

and ny = 2

= 6 x 27.8 x

Example:- Calculate the E between ground state and E2,2,1.

While

E = When more than one state has the same energy, the state is said to be degenerate. The number of states with the same energy is the degree of degeneracy. Example 2:- Calculate the energy in cm-1 of the first two energy levels of a particle in a box, and the energy difference E2-1 = E2 - E1 for :a/ an electron in a box 2Ao length. b/ a ball bearin of mass 1g in a box 10cm length.

E2-1 = E2-1 = ( a/ E = b/ E =

Example 3:An electron is confined to a molecule of length (1nm)(about 5 atoms long). What is a. Its minimum energy? b. Its minimum excitation energy from that state? Minimum energy is zero point energy when n=1 For a= 1 nm

The minimum excitation state E2-1 = = 1.8 x

A significant feature of the particle-in-a-box quantum states is the occurrence of nodes. These are points, other than the two end points (which are fixed by the boundary conditions), at which the wavefunction vanishes. At a node there is exactly zero probability of finding the particle. The nth quantum state has, in fact, n 1 nodes. It is generally true that the number of nodes increases with the energy of a quantum state, which can be rationalized by the following qualitative argument. As the number of nodes increases, so does the number and steepness of the `wiggles' in the wavefunction. It's like skiing down a slalom course. Accordingly, the average curvature, given by the second derivative, must increase. But the second derivative is proportional to the kinetic energy operator. Therefore, the more nodes, the higher the energy. This will prove to be an invaluable guide in more complex quantum systems.

Free-Electron Model The simple quantum-mechanical problem we have just solved can provide an instructive application to chemistry: the free-electron model (FEM) for delocalized -electrons. The simplest case is the 1,3-butadiene molecule

The four -electrons are assumed to move freely over the four-carbon framework of single bonds. We neglect the zig-zagging of the C-C bonds and assume a onedimensional box. We also overlook the reality that -electrons actually have a node in the plane of the molecule. Since the electron wavefunction extends beyond the terminal carbons, we add approximately onehalf bond length at each end. This conveniently gives a box of length equal to the number of carbon atoms times the C-C bond length, for butadiene, approximately 4x1.40Ao. Recall that 1 Ao=10-10 m, Now, in the lowest energy state of butadiene, the 4 delocalized electrons will fill the two lowest FEM \molecular orbitals." The total -electron density will be given (as shown in Fig. 4) by

A chemical interpretation of this picture might be that, since the -electron density is concentrated between carbon atoms 1 and 2, and between 3 and 4, the predominant structure of butadiene has double bonds between these two pairs of atoms. Each double bond consists of a - bond, in addition to the underlying -

bond. However, this is not the complete story, because we must also take account of the residual -electron density between carbons 2 and 3. In the terminology of valence-bond theory, butadiene would be described as a resonance hybrid with the contributing structures CH2=CH-CH=CH2 (the predominant structure) and oCH2CH=CH-CH2o (a secondary contribution). The reality of the latter structure is suggested by the ability of butadiene to undergo 1,4-addition reactions. The free-electron model can also be applied to the electronic spectrum of butadiene and other linear polyenes. The lowest unoccupied molecular orbital (LUMO) in butadiene corresponds to the n = 3 particle-in-abox state. Neglecting electronelectron interaction, the longest-wavelength (lowest-energy) electronic transition should occur from n = 2, the highest occupied molecular orbital (HOMO).

The energy difference is given by

Here m represents the mass of an electron (not a butadiene molecule!), 9.1x10-31 Kg, and L is the effective length of the box, 4x1.40x10-10 m. By the Bohr frequency condition

The wavelength is predicted to be 207 nm. This compares well with the experimental maximum of the first electronic absorption band, max 210 nm, in the ultraviolet region. We might therefore be emboldened to apply the model to predict absorption spectra in higher polyenes CH2=(CH-CH=)n-1CH2. For the molecule with 2n carbon atoms (n double bonds), the HOMO LUMO transition corresponds to n n + 1, thus

useful constant in this computation is the Compton wavelength 2.426x10-12m. For n = 3, hexatriene, the predicted wavelength is 332nm, while experiment gives max = 250 nm. For n = 4, octatetraene, FEM predicts 460nm, while max= 300 nm. Clearly the model has been pushed beyond it range of quantitative validity, although the trend of increasing absorption band wavelength with increasing n is correctly predicted. Incidentally, a compound should be colored if its absorption includes any part of the visible range 400-700 nm. Retinol (vitamin A), which contains a polyene chain with n = 5, has a pale yellow color. This is its structure:

Example : What is the probability of locating an electron between x=0 and x=0.2 nm in its lowest energy state in a molecule of 1nm length??

n=1 , z= 0.2nm p=0.05, or a chance of 1 in 20 of finding the electron in that region.

Example:The ground state energy for an electron in a 3Ao one dimentional box is 4 eV, the radius of hydrogen atom is 1Ao , suppose that the hydrogen electron is thought of as being in a three dimensional cubic box (1Ao one side ). Estimate the energy of H-electron on this basis.

n=1 = 27.8 eV for one dimension E = 3x27.8 = 83.4 eV for three dimension

Example :- calculate the wavelength of an electron having a kinetic energy of 4.55x10-25j.

Tunnelling
If the potential energy of a particle does not rise to infinity when it is in the walls of the container, and E < V, the wave function does not decay abruptly to zero. If the walls are thin (so that the potential energy falls to zero again after a finite distance), then the wavefunction oscillates inside the box, varies smoothly inside the region representing the wall, and oscillates again on the other side of the wall outside the box (Fig. 9.9). Hence the particle might be found on the outside of a container even though according to classical mechanics it has insufficient energy to escape. Such leakage by penetration through a classically forbidden region is called tunnelling. The Schrodinger equation Can be used to calculate the probability of tunnelling of a particle of mass m incident on a finite barrier from the left. On the left of the barrier (for x < 0) the wavefunctions are those of a particle with V = 0, so from eqn 9.2 we can write

The Schrodinger equation for the region representing the barrier (for 0 x L), where the potential energy is the constant V, is

We shall consider particles that have E < V (so, according to classical physics, the particle has insufficient energy to pass over the barrier), and therefore V - E is positive. The general solutions of this equation are

Uncertainty Principle of Heisenberg

This is an important feature of wave mechanics and discuses the relation between a pair of conjugate properties (those properties that are interdependent) of substance. According to the uncertainty principle, it is impossible to know simultaneously both the conjugate properties accurately. For example, the position and momentum of a moving particle are interdependent and thus conjugate properties also, they can not be determined with absolute exactness or certainty at the same time.

We have to point that there is a clear difference between the behavior of large objects like a stone and small particles like electron. The uncertainty product is negligible for large objects. For a moving ball of iron (wt=500g), the uncertainty expression.

Which is very small and negligible. But for electron of m = 9.1 x10-28g

This value is large in comparison with the size of electron and cannot be negligible.

Example:- Calculate the uncertainty in position of an electron if the uncertainty in velocity is 5.7x105 m.sec-1. Solution:

= 1x10-10 m Example:- The uncertainty in the position and velocity of a particle are 10-10m and 5.27x10-24 m.sec-1 respectively. Calculate the mass of the particle. Solution:

=0.1 Kg = 100 g

One dimensional box model is used to correlate the wavelength of maximum absorption of certain long chain dye molecules. A two dimensional box model gives quite good electron density distribution maps in aromatic systems. Three dimensional box problems are used in the derivation of the expression for the translational partition function in statistical mechanics.

Hermitian operators
Hermitian operators are very important in quantum mechanics because their eigenvalues are real. As a result, hermitian operators are used to represent observables since an observation must result in a real number. Examples of hermitian operators include position, momentum, and kinetic and potential energy.

OPERATORS AND EXPECTATION VALUES

Any hermitian operator, signifies a mathematical operation to be done on a wavefunction, which will yield a constant, o, if the wavefunction is an eigenfunction of the operator. ------- (1) Next the complex conjugate of the wavefunction, Equation -1 and integrated over all space. is multiplied to both sides of

If the wavefunction is normalized, then the integral leads directly to the value of the constant o.

is equal to one. This

--------- (2) As mentioned previously, the constant o corresponds to some physically observable quantity such as position, momentum, kinetic energy, or total energy of the system, and it is called the expectation value. Since the expression in Equation2 is being integrated over all space, the value obtained for the physically

observable quantity corresponds to the average value of that quantity. This leads to the fourth postulate of quantum mechanics. Example:Determine the average position any state (n). Solution/ for the particle in- a Box model problem for

This states that the average position of the particle is at the center of the box as it is predicted by classical mechanics. Example:- A particle limited to x-axis with between x=0 and x=1, elswhere. 1- Find the probability that the particle can be found between x= 0.45 and x=0.55. 2- Find the expectation value of the particles position. Solution 1/ probability = dx

Probability = = = 0.0251 a2 Solution 2/

Techniques of Approximation
There are very few problems for which the Schroedinger equation can be solved for exactly, so methods of approximation are needed in order to tackle these problems. The two basic methods of approximation are variation and perturbation theories. In variation theory, an initial educated guess is made as to the shape of the wavefunction, which is then optimized to approximate the true wavefunction for the problem. In perturbation theory, the Schroedinger equation is separated into parts in which the solution is known (from previously solved problems or model problems) and parts that represent changes or perturbations from the known problem. The wavefunctions from the part of the Schroedinger equation in which the solution is known are used as a starting point and then modified to approximate the true wavefunction for the Schroedinger equation of interest. Both theories are important and powerful problem solving techniques that will be used throughout the rest of the text. VARIATION THEORY The first step is to write the Hamiltonian for the problem. Then an educated guess is made at a reasonable wavefunction called formally the trial wavefunction, The trial wavefunction will have one or more adjustable parameters, that will be used for optimization. An energy expectation value ( eq. 2) in terms of the adjustable parameters, is obtained by using expectation equation (1) below:-

-------- (1)

----------(2) The term in the denominator of Equation -2 is needed since the trial wavefunction is most likely not normalized. Variation theory states that the energy expectation value is greater than or equal to the true ground-state energy, Eo of the system. The equality occurs only when the trial wavefunction is the true ground-state wavefunction of the system.

Since is a function of the yet undetermined adjustable parameters the value of can be optimized by taking the derivative of with respect to each adjustable parameter and setting it equal to zero. A value for each parameter is then obtained for the optimized energy of the ground-state.

-------------(3)
Variation theory can be proven as follows. Take the trial wavefunction, linear combination of the true eigenfunctions of the Hamiltonian . as a

Since is an eigenfunction of the Hamiltonian of the system, applying to will result in an energy eigenvalue En.

Completing calculation will give

Variation theory states that the energy calculated from any trial wavefunction will never be less than the true ground-state energy of the system. This means that the smaller the value of , the closer it is to the true ground-state energy of the system and the more represents the true ground-state wavefunction.

TIME INDEPENDENT NON-DEGENERATE PERTURBATION THEORY

The idea behind perturbation theory is that the system of interest is perturbed or changed slightly from a system whereby the solution is known. This can occur in two different ways: a) a new problem that has similarities to another system of which the solution is known (this happens often in chemistry) or b) the molecule or atom experiences some type of external perturbation such as a magnetic field or electromagnetic radiation (this is important in the case of spectroscopy). At this point the discussion will be limited to time-independent systems with nondegenerate quantum states. A time-independent perturbation is one in which the perturbation is not a function of time. The Hamiltonian for the system of interest is divided into parts: the part representing system with a known solution, and then into a number of additional parts that correspond to perturbations from the known system to the system of interest.

The term in the equation above with a superscript zero corresponds to the Hamiltonian for the system with a known solution (unperturbed system), (0). The rest of the terms correspond to additional terms that perturb the known system. The term (1) is a first-order perturbation, the term (2) is a second-order perturbation, and so on. The idea is that each order of perturbation is a slight change from the previous order.