The Theory of the Chemical Bond: A Textbook for Chemistry 2160

Stephen Lee Department of Chemistry and Chemical Biology Cornell University, Ithaca, NY 14853-1301 September 4, 2009

Chapter 1 What this book is all about

I write this book with Chemistry 2160 students, second semester rst-year honors chemistry students, in mind. Every year around 100 of the most motivated freshman chemistry students here at Cornell take this course (we have some 1500-2000 freshman chemistry students in total). The students in this class are self-selected but they are among the brightest students we have. Usually more than three-quarters of the students in the class have received a 5 on the AP exam. When I ask the students of the class what their future plans are, typically a third of the students say they plan on becoming engineers, a third doctors, and a third scientists. They are an exciting group of students to teach: they represent the future of technology in the United States. This course generally receives bi-modal ratings from the students in their course evaluations: some students view the course favorably (5s and 4s) and others as an unpleasant experience (1s and 2s). Many of the students who give favorable ratings to this course become chemistry majors. If you are a rst year student taking Chemistry 2160, here are some thoughts about what will happen in this course. Things are going to be dierent. While students often feel that Chem 2150 was an extension of AP high school chemistry, the same will not be the case this

semester. This course, instead of looking back to your past experiences in chemistry, looks ahead to your future experiences. Chemistry is a big subject: three of its main elds are organic (second year chemistry), physical (third year), and inorganic (fourth year). Students who take these upper level chemistry classes can nd the material covered in organic, physical and inorganic chemistry strangely disconnected. They are disconnected to the point that it may seem that organic and physical chemists belong in disparate worlds. The Cornell chemistry faculty would not be doing a good job of preparing you for our discipline, if we did not try to help you unite these elds in your own minds. You, as the student, will need to carry the responsibility here at synthesizing your knowledge, but it is my hope that this course will provide you with some of the essential tools to do so. If you are not planning on taking more chemistry courses do not worry. Many, in fact most, of the students who have come back to talk to me about this course, turn out not to be chemists at all. For the rst time, in the last year, three former students, who are now in nance, have come by to talk about this class. All three told me the same thing: they nd themselves thinking about the contents in this course. As one of them said to me, It sticks. I like to think that this course has made these students happier and maybe even more successful in their nancial careers. Whatever your nal eld may be, I hope it will serve the same role for you.

1.1

What you will learn if you study this book

This book describes, in the plainest language I know, my understanding of the chemical bond. The chemical bond lies at the heart of all chemistry. If you understand the chemical bond, you will know about one theme which unites organic, physical and inorganic chemistry. While the chemical bond is a universal and timeless truth, the human understanding of the chemical bond changes with each generation of scientists. Linus Pauling wrote a famous

book (based on lectures given here at Cornell) fty years ago, The Nature of the Chemical Bond. Much of the content of this course is not covered in this landmark book. To give you some understanding of our uxional understanding of the chemical bond, when I took freshman chemistry, I was taught there were three types of strong chemical bonds: the covalent, the ionic and the metallic. In this book we will discover that the metallic bond and the covalent bond can be productively treated in a single unied approach. So for this course, we will need discuss only two types of chemical bonds: covalent and ionic bonds. In this book you will learn the quantum mechanical basis of the covalent bond and the electrostatic nature of the ionic bond. Of the two, the covalent bond is much more dicult to understand. To understand the covalent bond you will need to learn about the electron, quantum mechanics, the virial theorem, and molecular orbital theory. For the ionic bond, we can rely on a classical sense of the material world. Due to the necessary ground-work required for the former subject, the bulk of this course will be devoted to the covalent bond. Only in the last 10-15% of this course will we consider ionic forces. None of the ideas in this book were originally created by my research group. I can claim no original credit for anything in this book. Roald Homann, Kenichi Fukui, David Pettifor, and Klaus R denberg gure among the many chemists and material scientists whose key u ideas are incorporated in this book. I do not propose, nor am I capable of, giving an accurate scientic bibliography for each of the subjects covered in this book. Instead at the end of each chapter a few texts or articles are listed which could help enrich your understanding of the given material. Such references will be kept at a minimum, so as to not overwhelm the student. Problem sets and old exams will also be given.

1.2

This book is not a textbook

As a student in this class, I hope to take you out of your comfort zone into places where you will not be familiar. If we (the teaching sta and the students together) are successful, everyone in this class will see unfold a rich and challenging view about how the material universe around us behaves and how this material universe is based on the chemical bond. While this book is hopefully a guidebook, it is not a textbook. Textbooks tend to have numerous editions and are based on a collective knowledge of the eld. They contain the promise within them, that if you just follow the textbook, you will gain mastery of the subject. My own personal experience was that the textbook approach, rarely worked. Followers do not become masters and teaching-learning is at its core a one-onone activity. When I was a student, every now and then I would nd a book where I had the sensation the author was trying to explain to me a full subject, as they understood it to be. The books unfolded like stories. The story could have been thermodynamics (Enrico Fermis book with this same title), or regular polytopes (Coexters book). These books worked for me. I didnt do very well in rst year physics, but I certainly got every exam question on thermodynamics correct. While this book will not come close to the clarity of the classics, I hope that its intent can be the same. I would like you the student to get wrapped up in a story, the story of the chemical bond. Follow the story as I tell it, but challenge the story as well. Before every lecture read ahead the chapter or chapters in the book which the lecture will cover. Find out which ideas make sense to you and which do not. Try to gure out the chain of logical thought, which the book and the lectures are trying to express. A site will be placed in the Cornell course web site, Blackboard, for you to post your questions. To encourage you to post thought provoking questions, the best questions will be awarded 1 or 2 extra credit points. Chemical errors in the book noted in Blackboard before

the relevant lecture will also receive 1 point. (The course total is 500 points). I will try to answer the Blackboard questions in class, but if you nd the classroom lecture still does not make sense, speak up. Please feel free to ask questions in class. After the lecture, review what it is you heard, and what it is you understand. Start doing the problems relevant to the material. Think of how this material relates to other material in the course. If you can, make up your own problems. Exams in this course are my questions to you. In the best of all possible worlds, exams are learning experiences. I will try to design exams which test how well you see how the course material is put together: how the course material can be used in dierent ways. On every exam, there will be at least one question which will place two separate concepts of the course into a single explicit problem. I will know we, the teaching sta of this course, have succeeded as teachers, if you as a student can start thinking of such questions yourself.

Chapter 2 The electron

To understand the covalent bond, one must understand the electron. We therefore begin our course by stating facts about electrons, some, but not all, of which you will have seen in high school AP chemistry.

2.1

Orbitals

Electrons in atoms lie in orbitals. The word orbital was originally chosen for its similarity to the word orbit. Just as planets move around the sun, electrons move around the nucleus, see Figure 2.1. The planetary analogy for electron motion has many virtues. The electron has a small mass compared to the nucleus and lies in the electrostatic potential well of this nucleus. In exactly the same way a planet has a small mass when compared to the mass of the sun, and the planet sits in the gravitational potential well of the sun. Even the relation describing electronic and planetary potential energies are the similar.

mE mS r

Figure 2.1: Planetary vs. electronic motion

where U, mE , mS , and r are respectively the gravitational potential energy, the mass of the earth, the mass of the sun, and the distance between the earth and the sun. Analogously, the potential energy of an electron in the electrostatic well of a nucleus obeys the relation: q q+ r

where q , q+ , and r are respectively the charge of the electron, the charge of the nucleus and the distance between the electron and the nucleus. The analogy between orbits and orbitals bears one main strength and one main weakness. First, the strength. In both planetary orbits and electron orbitals, the concepts of potential and kinetic energy can be exactly dened. Potential energy is the U value given in the equations above. Kinetic energy is
p2 , 2m

where p is the momentum and m the mass.

(Classically, the momentum is dened to be p = mv, where v is the velocity.) The Virial Theorem: On a per kilogram basis, the further away a planet is from the sun, the less gravitational potential energy it has. Per kilogram, Mercury has the most negative solar gravitational potential energy, while Pluto, the farthest planet from the sun, has the 7

least negative. But there is another compelling trend to planetary energies. In Table 2.1 we list average planetary velocities. The farther a planet is from the sun, the slower it moves. Pluto, 100 times futher from the sun than Mercury, travels at one tenth Mercurys speed. Pluto therefore not only has a less negative potential energy than Mercury, but less kinetic energy as well. Planetary motion obeys the Virial Theorem, a theorem which says that there is a xed relation between potential and kinetic energy. For motion like planetary motion, the virial theorem states: 2T = U where T and U are respectively the kinetic and potential energies. Table 2.1: Planetary Orbital Properties. Mean Distance from Sun (km) Mean Velocity (km/s) 5.8 107 48 1.1 108 35 1.5 108 30 8 24 2.3 10 7.8 108 13 1.4 109 10 2.8 109 6.8 4.5 109 5.4 9 5.9 10 4.7

Planet Mercury Venus Earth Mars Jupiter Saturn Uranus Neptune Pluto

Electrons in stable orbitals obey the virial theorem: Electrons in stable orbitals, just like planets in stable orbits, obey the virial theorem. The closer an electron lies to the nucleus, the more negative is its potential energy. According to the virial theorem, the more negative the potential energy, the faster the electron moves. In Au, for example, there are electrons which lie very close to the nucleus. The electron orbital closest to the nucleus is called the 1s orbital. As the Au 1s orbital lies close to the nucleus, electrons in this orbital move fast: Au 1s orbital electrons move at 0.6 times the speed of light. In the hydrogen atom by contrast, where the 1s orbital is much farther from the nucleus, electrons move 8

much slower, at only

1 137

times the speed of light. This latter number is so useful, it has a a

name, the Fine Structure Constant. It plays an important role in physics. Electrons do not lie in orbits: The orbit-to-orbital analogy has one major breakdown. Electrons are best described with quantum mechanics while planets are best described by classical mechanics. Rather than thinking of planetary orbits, where the planets maintain a more or less xed distance from the sun, electrons in the course of their motion vary their distances from the nucleus.

Figure 2.2: y trajectory vs. y probability distribution

Comparison of electrons to ies: A qualitative picture might be useful here. A good picture for an electron circling a nucleus might be a housey circling a plate of food. The y (the electron) in its lowest energy state ies close to the plate of food (the nucleus) and sometimes alights on the plate itself. In describing the ys position it is useful to envision a probability function. This function gives the relative probability that the electron is located at a given place, see Figure 2.2. As the Figure shows, the most probable place the y would be located is directly on top of the plate of food. As the distance from the plate of food increases, the probability decreases. This distribution is more or less the least energetic prole of a non-sleeping y. We call the lowest possible energy probability distribution the ground state distribution. For atoms which have just one or two electrons the ground state distribution for the electron is always the 1s distribution. For historical reasons, the 1s distribution is typically called 1s , where is the Greek letter rho. Excited state distributions: We can also envision excited state distributions. As the name implies the excited state is a distribution of higher energy than the ground state distribution. Both ies and electrons can enter excited states. Once one disturbs a y, for instance by trying to kill it, it ies in a much more erratic and energetic manner. It ies much farther from the plate of food and typically no longer lands on the food plate. Electrons, like ies, also have excited states. In the 2p orbital, one of the most important higher energy states of an electron, the electron lies further from the nucleus than an electron in the 1s orbital. Just like in the y excited state, if the electron enters the 2p orbital, the electron is never found on the center of the distribution. (One major dierence between an excited y motion and an excited electron motion is that while the y always ies faster in its excited state, the electron ies slower.) The 2p distribution is called 2p . Both the 1s and 2p distributions are stable distributions: electrons can, under the right circumstances, stay in these distributions for long periods of 10

Figure 2.3: Ground state and excited state y vs. 1s and 2p electron probability distributions

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time. Potential energy and electron distributions: From electron distributions we can deduce potential energies. At this early stage in your technology career, you may only be able to deduce qualitative potential energy trends (later, once you know integration you will be able to get exact numerical answers). For now, compare the 1s and 2p distributions shown in Figure 2.3. In the former distribution, the electron on the average lies much closer to the nucleus than for the latter distribution. Recalling the numerical expression for the electrostatic energy, U
q q+ , r

and noting that

r on the average is smaller for the 1s distribution, while q+ (the nucleus) is a positive number, while q (the electron) is a negative number, we nd the value of U more negative for the 1s state than the 2p state. We can similarly compare most pairs of electron probability distributions. This comparison is important. For example, if we know the relative potential energies, by applying the virial theorem we know relative kinetic energies. As the total energy is the sum of the kinetic and potential energy, we can further deduce relative total energies. Electrons in unstable distributions: Unfortunately, the virial theorem only applies to stable electron orbitals. Thus while in all cases we can deduce the electrostatic potential energy, in general, for unstable electron orbitals, knowing just the electron probability distribution alone, we know nothing either about the kinetic or the total energies. In such cases, we must go beyond the electron probability distribution.

Electrons obey quantum mechanics: Electrons obey quantum mechanics. In quantum theory, the kinetic energy of an object can be determined by knowing its wavefunction. Wavefunctions, generally denoted by , the Greek letter psi, are related to the probability

12

Figure 2.4: 1s and 2p wave functions and probability distributions

13

density by the relation: 2. The wavefunctions of the 1s and the 2p orbitals are shown in Figure 2.4.

Figure 2.5: 1s and 2p wave functions and waves with similar wavelengths

Electrons are waves: The wavefunctions 1s and 2p bear a qualitative similarity to waves. The waves closest in appearence to the two wavefunctions are shown in Figure 2.5. 14

Let us consider the two waves shown in this Figure. Both waves have a wavelength. We call these wavelengths 1s and 2p , where is the Greek letter lambda. In quantum mechanics there is a xed relation between and kinetic energy. For particles moving at or close to the speed of light Trel 1

while for particles moving signicantly slower than the speed of light 1 . 2

Tnonrel

The subscripts rel and non-rel refer to relativistic and non-relativisitic. (Scientists generally use these terms to distinguish objects which are moving close to or far away from the speed of light.) The electrons vital to chemistry lie far away from the nucleus and hence have slow speeds, speeds signicantly less than the speed of light. In chemistry the latter equation is therefore much more important. For the 1s and 2p orbitals, 1s is shorter than 2p . By the equation above, the 1s state therefore has more kinetic energy. Both the 1s and 2p orbitals are stable electron states. They both therefore obey the virial theorem. We conclude that the 1s state has a more negative potential energy than the 2p state: the same conclusion as we found from considering the two electron probability distributions.

2.2

Appendix: Angular Momentum

We conclude this chapter with an examination of angular momentum and its connection to the total energy of both orbits and orbitals. We begin with orbits. The results we obtain about planetary orbits orbits proves relevant to stable atomic orbitals.

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Figure 2.6: The position, r, velocity, v, and angular momentum, L, vectors

Planetary picture of angular momentum: In Figure 2.6 we re-illustrate planetary motion, where the position vector, r; the velocity vector, v; and the angular momentum vector, L, have been added on. The position vector, r, describes the arrow pointing from the sun to the planet. The velocity vector, v, is an arrow describing the direction of motion of the planet. (The direction of the arrow v gives the direction of travel at a given time; the length of this same arrow is proportional to the speed of the planetary motion at the same given time.) Angular momentum is also a vector. As the Figure shows, angular momentum can be represented by an arrow which is simultaneously perpendicular to both r and v. Furthermore, if r and v are mutually perpendicular, the length of the arrow L is proportional to the length of r times the length of v. These relations are expressed by the formula L = mr v, where m is the mass of the planet and is the vector cross product.

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Relation between angular momentum and stable orbitals: The angular momentum is therefore completely determined by knowledge of r and v. In Table 2.1 we listed the magnitudes of r and v for the nine planets. Applying the formula above to the values in this Table, we can deduce the angular momentum for one kg of any of the listed planets. We leave this task to the student. We note the chief nding of such a calculation: the farther a planet lies from the sun, the greater is its angular momentum. (One of the problems at the end of this chapter asks the student to conrm that this fact is a consequence of the virial theorem.) Applying the virial theorem to angular momentum: In summary, the greater the value of r, the greater the angular momentum, L. Conversely the greater the value of L, the greater the value of r. From the virial theorem, we know the greater the value of r, the less negative is the potential energy, U, and the less the value of the kinetic energy. We conclude, the greater the value of L, the less negative is the value of the total energy. This result is absolutely true for planetary orbits. As our primary interest is electrons in orbitals, we note here the principal nding for orbitals: for all atoms and ions with more than a single electron to them, increases in the angular momentum lead to less negative total energies.

2.3

Problems

1. Based on the virial theorem prove or disprove the following statement. For an atom with an electron, the total energy of the electron can never be positive. 2. In outer space, there is a single proton. A million miles from this single proton is a single electron travelling at one-thousanth the speed of light. Does this situation prove that the virial theorem is sometimes false. If not, why not. 3. One curious feature of the 1s and 2p probability distributions is that at distance r = 0 17

the former function has a non-zero value while the latter function is exactly zero. We will learn later that the angular momentum of an electron in the 1s state is zero while an electron in the 2p state is not zero. Show why the values of the angular momentum cause 2p to be equal to zero at r = 0. 4. The next more excited state (ie., even higher energy state) than the 2p state is the 3d state. Draw two fundamentally dierent possible qualitative pictures of both 3d and 3d . For the sake of comparison draw on the same page 2p and 2p . 5. Angular momentum is a conserved quantity. Deduce from this fact that all planetary motion is planar. 6. Both linear momentum and energy are functions of the mass and velocity. Compare an adult man walking at 3 miles an hour, a baseball thrown at 50 miles per hour and a bullet travelling at 1000 m/s. Estimate the kinetic energy and the momentum of these three without looking up any information on the internet. Which has the greatest momentum and which has the greatest kinetic energy? Without looking up any information on the internet, to one signicant gure what is the conversion factor between miles per hour and meters per second? 7. An atom is composed of a nucleus and its electrons. At room temperature a nucleus has roughly two and a half kJ (kiloJoules) of kinetic energy per mole. Electrons are travelling at one one-hundreths to one-tenth the speed of light. What is the order of magnitude of the ratio of the kinetic energy for the electrons vs. the nucleus in a carbon atom? 8. A planet of mass m is travelling in a circular orbit at a distance r from a sun of mass M. The gravitational constant is G, ie., U = G mM . Write an expression for the angular r momentum of this planet using only the variables M, m, and r and the constant G. 18

9. In the above problem we assumed that the planet was travelling in a circular orbit around the sun. Actually both the sun and the planet are travelling in circular orbits around their center of mass. Let r and R be respectively the distances the planet and the sun are from their center of mass. Further assume that the planet, the center of mass, and the sun lie at all times in a straight line. Express R as a function of m, M, and r. Assume the center of mass is motionless. Using the law of the conservation of linear momentum, write an expression for the speed of the sun, V , as a function of just m, M and the speed of the planet, v. What is the ratio of the kinetic energies of the sun and the planet? What variables control this ratio? 10. In the above problem you calculated both the ratio of r and R as well as v and V assuming that the sun and the planet stay in a straight line. Are your calculated values of these two ratios compatible with this assumption? 11. If the absolute temperature is halved, the kinetic energy of the nucleus is halved, but the kinetic energy of the electrons remain essentially the same. In what way are the results of the previous two problems in contradiction with this fact?

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Chapter 3 Electron orbitals and the periodic table

In this chapter we will make a number of striking statements about electron orbitals. The facts themselves are so peculiar that I worry that it will be hard for you, the student, to make much sense of them. They are, however, (for the most part) facts (1) which freshman chemistry students typically have to memorize in standard freshman chemistry courses and (2) which allowed scientists for the rst time to understand the organization of the periodic table (these facts are therefore important to chemistry as a whole). In this chapter we will give as plain a rendering of these facts as possible. We reserve for subsequent chapters explanations as to where these facts come from and how these facts can be related to the wave-like nature of electrons. Quantum numbers: All electrons in atoms lie in an orbital, a wave function. Such orbitals are called atomic orbitals. All stable atomic orbitals can be described by four dierent quantum numbers. A quantum number is a kind of physical constant. All quantum numbers are unitless.

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When scientists speak of constants they have two dierent constants in mind. On the one hand there are constants like the speed of light or the rest mass of the electron. These are constant numbers: neither the speed of light nor the rest mass of an electron ever changes. But scientists speak of another kind of constant. In unperturbed collections of physical objects (such collections are called systems) quantities such as the total energy or the total momentum do not change. These latter constants, are constant only so long as the system is unperturbed. To distinguish these constants from the xed constants (such as the speed of light), scientists call these latter constants conserved quantities. Quantum numbers are conserved quantities. As long as an electron in an orbital with assigned quantum numbers is unperturbed neither by other atoms nor receives nor emits light, the quantum numbers of the electron stay xed. Principal quantum number: The rst quantum number is n, the principal quantum number. The principal quantum number is always a positive whole number. The lowest possible value for n is 1. For all atoms and all ions there is at least one atomic orbital for each value of n. Of all the quantum numbers, it is the principal quantum number which gives the most information about the energy of the orbital. For atoms and ions with just a single electron (H, He+ , Li2+ , etc.) the relation between the principal quantum number and the total energy is a precise one: En = ZRH , n2

where Z is the nuclear charge (Z = 1 for H, 2 for He, and so forth) while RH = 2.2 1018 J. While for atoms with more than one electron, the relation describing the total energy is a more complicated one, n remains a dominant energetic variable.

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3.1

Orbital angular momentum

Orbital angular momentum quantum number: The orbital angular momentum quantum number, l, is a whole number which ranges in value from 0 to n 1, where n is the principal quantum number. Thus for an n value of 1, the only possible value of l is l = 0; for an n value of 2, l = 0 or l = 1; and for an n value of 3, l = 0, l = 1 or l = 2. From the text above, we have the sense that the principal quantum number tells us something about the energy of an electron. The orbital angular momentum quatum number tells us about another physical quantity, the angular momentum. The l quantum number is suciently important in chemistry that each of the values of l have specic names. l = 0 orbitals are called s orbitals; l = 1 are p orbitals; and l = 2 are d orbitals. Chemists typically designate orbitals by a combination of the principal and orbital angular momentum quantum numbers. For example, the 2p orbital refers an orbital where n = 2 and l = 1; The 3s orbital refers to n = 3 and l = 0. The relation between l and L: In the case of the principal quantum number, n, one can write an exact equation relating total energy to n, only for atoms or ions with exactly one electron. For the case of the orbital angular momentum quantum number, l, the total orbital angual momentum is exactly determined for all atoms and ions. The formula relating l to L is L2 = h2 l(l + 1), where h is Plancks constant divided by 2 and where L = |L|. Plancks constant: Plancks constant is one of the most important constants in physical chemistry. Its value is: h = 6.6 1031 kJ s; if one divides h by 2 one obtains h, h = 1 1031 kJ s. The units of Plancks constant are of interest. We derive these units by examining the equation relating L2 and l. As l is unitless and L2 is in units of angular 22

momentum squared, the equation L2 = h2 l(l + 1) tells us that h is in units of angular momentum. As we shall see later, Plancks constant will give us the order of magnitude of many of the basic angular momentums found in chemistry.

Figure 3.1: The relation between E and l for several dierent atoms.

Relating l to the total energy: The greater the value of l, the greater the value of L. We now make the connection between L and the total energy,E. To make this connection, we invoke the similarity between electron orbitals and planetary orbits. For planets in stable orbits (see the Appendix of the previous chapter), the greater the value of L, the greater is the total energy. This statement is also true for atoms, but with one proviso: the atom or ion in question must have more than one electron. Thus, for all atoms with more than one electron, the greater the value of l, the greater the value of L; and the greater the value of L, the greater is the value of E. Thus the 2p orbital has a less negative total energy ( a less negative energy is a greater energy) than the 23

2s orbital; similarly the 3d has higher energy than 3p which is higher in energy than 3s. Examples of these trends are shown in Figure 3.1. Summary of the relation between n, l and the total energy: In the absence of a magnetic eld, for atoms and ions with just a single electron to them, the total energy, E, is independent of l and depends solely on n: the greater the value of n, the less negative is the total energy. In the absence in a magnetic eld, for atoms and ions with more than a single electron, the total energy, E is solely a function of n and l. For a xed value of l, the greater the value of n, the greater is the total energy; similarly, for a xed value of n, the greater the value of l, the greater the total energy.

Figure 3.2: A schematic for the Aufbau principle.

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The ordering of the atomic orbitals: The ordering of the energy of atomic orbitals follows a straight-forward mnemonic, see Figure 3.2. For all atoms with more than one electron, the lowest energy orbital is 1s. The energies of the orbitals then follow in the sequence 2s, 2p, 3s, 3p, 4s, 3d, etc. As the Figure shows, the energies of the orbitals follow a sequential pattern most easily discerned with the diagonal lines of Figure 3.2.

3.2

Directional orbital angular momentum

The third quantum number is the directional orbital angular momentum, ml . The value of ml is restricted to being the integers which range from l to l in value. Thus for all s orbitals, where l = 0, ml = 0, while for p orbitals, where l = 1, ml can have one of three values: -1, 0, or 1. Origin of ml : The ml quantum number is derived from the vector nature of the angular momentum. While the l quantum number determines the magnitude of the angular momentum, it tells us nothing of the direction of the angular momentum. The most illuminating example are the p orbitals, where l = 1. We enumerate here the L which correspond to the quantum numbers ml = 1, 0, or 1. The magnitude of L is xed by the formula L2 = h2 l(l + 1): for l = 1, L = 2 . However, the direction of L changes: ml = 1 corre h h h sponds to L = (0, 0, 2 ); ml = 1 to L = (0, 0, 2 ); and the ml = 0 state refers to a specic, but here unspecied, vector perpendicular to the previous two vectors. ml is a conserved quantity: In the absence of any magnetic eld, ml is always a conserved quantity. ml can furthermore remain a conserved quantity if the external magnetic eld is aligned in an appropriate direction. For example, in the previous example of p orbitals, whose ml were given with respect to the z axis, if the magnetic eld is aligned in the z direction, the ml quantum number remains conserved. 25

Figure 3.3: The energies of ml = 1, 01 as a function of the external magnetic eld strength, B.

Figure 3.4: Three possible orientations for an l = 1 electron.

The relation between ml and the energy: The quantum number ml aects the total energy only in the presence of an external magnetic eld. Referring again to the previous example where l = 1 and the magnetic eld is aligned along the +z axis, the ml = 1 state is lowest in energy, the ml = 1 is highest in energy, while the energy of the ml = 0 orbital is unchanged. These qualitative results are shown in Figure 3.3, where the energy levels of 26

the ml = 1, 0, 1 states are plotted as a function of the strength of the magnetic eld. These results can be understood by thinking of a classical charge moving in a xed circular orbit. We can imagine three such cases: the charge has an angular momentum parallel, perpendicular and anti-parallel to the direction of the magnetic eld (which for convenience, we place into the z direction, see Figure 3.4. We consider now just the case where the charged particle has an angular momentum parallel to the direction of the magnetic eld. In such a case, L = (0, 0, L). In a classical picture the energy of such a charged particle would lowered by the magnetic eld. We now turn to the electron with the angular momentum (0, 0, L) as is found in the ml = 1 state. As Figure 3.3 shows, just as in the classical picture, the quantum mechanical electron behaves in exactly the same way. Similar arguments can be applied to the ml = 0 and 1 orbitals.

3.3

Directional spin quantum number

Electron spin quantum number Independent of an electrons spatial orbital, an electron always has an internal angular momentum called its spin. This angular momentum carries the spin quantum number s = 1/2. The spin quantum number while unitless, is half-integral in value. The relation between s and the spin angular momentum, S is the same as is found between l and L: S 2 = h2 s(s + 1). As the s quantum number is always xed to the value of 1/2, the value of S for an electron is also always xed at 3 /2. S and s both being xed, chemists rarely concern themselves h with this quantum number. Directional spin quantum number: Just as in the case of of orbital angular momentum, where we could further consider directional orbital angular momentum, we can consider the

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directional spin quantum number, ms . In just the same way that the ml quantum number is limited by l, the ms quantum number is limited by s. ms can range in values from ms to +ms , where values of ms must dier from each other by whole numbers. As in our case s = 1/2, the quantum number ms has two possible values 1/2 and +1/2. Recalling that h the magnitude of S is 3 /2. The value ms = 1/2 corresponds to the S = (0, 0, 3 /2) and h the value ms = 1/2 corresponds to a vector pointing in the opposite direction. The number of atomic orbitals with the same value of n and l: In the absence of a magnetic eld, neither ml nor ms play any role in either the total angular momentum or the total energy of an electron. While ml and ms do specify the direction of the orbital and spin angular momenta, for chemists, the most important feature of these two quantum numbers is that they in addition specify the number of orbitals which have a given value of n and l. Take for example the 2p or the 3p states. In both cases l = 1 and ml ranges over the values of 1, 0, or -1. ms has the value 1/2 or -1/2. A 2p or 3p electron therefore has simultaneously one of the possible three ml values and one of the two possible ms values: a total of six possibilities. A d orbital, with l = 2 has simulanteously both one of ve possible values for ml and one of the two possible values of ms : a total of ten possibilities.

3.4

Electron orbitals and the periodic table

The four quantum numbers (n, l, ml , and ms ) specify completely a stable atomic orbital. These numbers are called quantum numbers as they relate to the quantum mechanical properties of electrons. It may not be suprising therefore, that to learn about the important role these numbers play in chemistry, the student will need to learn some additional facts about quantum mechanics.

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Identical particles: In quantum mechanics, a group of electrons are identical to one another. Consider two electrons (lets call then A and B) and even let these two electrons have dierent quantum numbers, ie., lie in dierent orbitals: once they come together in an atom, it is none-the-less impossible to distinguish electron A from electron B. All particles which have this sort of property are called identical particles. Fermions and bosons: There are two types of identical particles: fermions with halfinteger spin (an electron with s = 1/2 is a fermion) and bosons with integer spins (a photon, where s = 1 is a boson). Fermions obey the Pauli exclusion principle: only one electron can have one complete set of four quantum numbers at a given time. Fermions with a given set of quantum numbers exclude all other identical particles from the state which they occupy. (By contrast, bosons draw other identical bosons into the same orbital: lasers, superconductors and superuids are all examples of boson attraction.) The Aufbau principle: In Figure 3.2, we gave the energy ordering of the various atomic orbitals. We can combine this ordering with the Pauli exclusion principle. Consider for example an atom with two electrons. In a stable arrangement of the atom, these two electrons will occupy the lowest energy orbitals. Two electrons can occupy the 1s orbital. One of the two electrons has ms = 1/2, the other has ms = 1/2. The atom with two electrons is He, helium. As the arguments above demonstrate, He has two electrons in the 1s orbital. Consider now an atom with 10 electrons. The two lowest orbitals are 1s and 2s. Each of these orbitals can take one up-spin (ms = 1/2) and one down-spin (ms = 1/2) electron: a total of four electrons. The next lowest orbital is 2p. In this orbital ml can take one of three values and ms on of two values: a total of six possibilities. Thus there can be six electrons in the 2p state. The atom Ne, neon, with ten electrons has all 1s, 2s, and 2p states lled. Both the He and Ne examples are examples of the Aufbau principle: the principle in which the Pauli exclusion principle is coupled with the energy requirements of the dierent orbitals. 29

Electron congurations: The electron orbital occupations play a dominant role in the chemistry of the elements. Chemists represent these occupations in a number of dierent ways. We illustrate two of the most important dierent ways here. The rst method is to list the occupied orbitals in sequential order. For example for Ne the sequential ordering is 1s2 2s2 2p6 , while F, uorine, with nine electrons is 1s2 2s2 2p5 , where the superscripts indicate the number of electrons occupying a given orbital.

Figure 3.5: Three possible AO diagrams for the uorine atom. The picture on the right is the valence atomic orbital diagram.

Atomic orbital diagrams: Even more important for this course are atomic orbital diagrams. Atomic orbital diagrams, AOs, list a portion of all the occupied and unoccupied atomic orbitals. Three examples of the F AO diagram are shown in Figure 3.5, Note in the AO diagram, we list a series of occupied and unoccupied atomic orbitals. It is not necce30

sary to list all the occupied and unoccupied orbitals. The third example shown is the most commonly used. We speak more of this third example in the next two paragraphs. Valence, core and excited-state orbitals: The electron conguration notation listed above becomes quite cumbersome for atoms with a large number of electrons. Consider iron, Fe, with 26 electrons. If we were to represent its full electron conguration it would be 1s2 2s2 2p6 3s2 3p6 4s2 3d6 . Chemists often will abbreviate this series by stating explicitly only those orbitals occupied after the last preceding noble gas element. In the case of Fe, the last noble gas conguration lled is argon, Ar (Ar has 18 electrons). Chemists will therefore write the Fe electron conguration as [Ar] 4s2 3d6 . Chemists call the orbitals lled up to the last lled noble gas conguration core orbitals. Chemists further dierentiate orbitals which lie above the last lled noble gas conguration into one of two types. The lowest energy of these orbitals are called valence orbitals. The nomenclature of valence orbitals is somewhat vague. However, as a good rule-ofthumb, the valence orbitals are those orbitals which come between the last lled noble gas conguration and the next not-completely-lled noble gas conguration. Thus is the case of Fe, valence orbitals could be taken to be the 4s, 3d, and 4p orbitals. Orbitals which lie above both the core and valence orbitals are called excited state orbitals. In a stable arrangement of an atom, core orbitals are always lled; valence orbitals are sometimes lled; and excited-state orbitals are never lled. In Figure 3.5a, the core, valence and some of the excited state atomic orbitals were shown; in Figure 3.5b, just the valence and some of the excited-state atomic orbitals were given; and nally in Figure 3.5c, we show just the valence atomic orbitals. This nal diagram is the valence atomic orbital diagram.

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Figure 3.6: The relation between the periodic table and the Aufbau principle.

The periodic table: All chemistry students in this course have seen the periodic table. As a student you may have wondered at its unusual format, with short rows at the top and long rows on the bottom. We are now poised to understand the shape of the periodic table. In Figure 3.6 we present a periodic table based on the consecutive lling of atomic orbitals. First lled is the 1s orbital, then the 2s, and so forth. The number of elements for each value of n and l depends on the number of possible dierent values of ml and ms . It may be seen that the shape of the periodic table is determined by the four atomic quantum numbers coupled with the Pauli exclusion and Aufbau principles.

3.5

Conclusions

This chapter has demonstrated that if all atoms have four quantum numbers, and if the counting principle developed for these four quantum numbers is correct, then the quantum numbers play a role in the periodic structure of the elements. We conclude this chapter by

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examining this proposition more fully. From previous chemistry courses, you have learned that elements lying in the same column of the periodic table often have similar chemical properties. For example, examine column 14 of the periodic table. In this column, the elements carbon,C; silicon, Si; and germanium, Ge lie one beneath the other and all have similar chemical properties. Examining Figure 3.6, we see that for each of these three elements, the valence orbitals all have dierent n quantum numbers, but the same l quantum numbers. We conclude that it is the l quantum numbers which play the greatest role in periodic trends, while the n quantutm number is of less importance. We further conclude that the ml and ms quantum numbers also play a role in atomic properites. In the case of the chemically similar C, Si, and Ge exactly two of the six possible valence p orbitals (and all the valence s orbitals) have been occupied. We deduce the number of occupied s and p orbitals is important. And if this is so, it is reasonable to assume that each of occupied valence p orbitals are based on the same combination of ml and ms states. In the next chapter, we consider an explicit spatial represention of these ml and ms combinations. Giving a spatial shape to each of these orbitals will allow us rst to make the bridge from quantum numbers to the shape of orbitals, second determine the connection between the shape of orbitals and the shape of stable molecules, and nally understand the relation between the shape of molecules and chemical reactivity.

3.6

Problems

1. Based on the Aufbau principle, draw a qualitative Atomic Orbital diagram of iron. Include the 1s 2s, 2p, 3s, 3p, 3d, 4s and 4p orbitals in your picture. 2. Draw a quantitatively accurate atomic orbital energy diagram for Li2+ , including the 1s 2s, 2p, 3s, 3p, 3d and 4s orbitals. Label axes and state numerically the actual 33

energies of the orbitals. Compare this diagram to the diagram of neutral lithium, see Figure 3.1. Does Li2+ obey the Aufbau principle as stated in Figure 3.2 ? 3. Monochromatic light has a xed frequency, see Figure 3.7. The frequency of this light, is related to the energy of one photon of light by the formula E = h. The frequency of light is also related to the wavelength and speed of the light, respectively and c by the formula c = . Calculate the order of magnitude of energy of one mole of photons of low energy ultra-violet light. A Joule is the kinetic energy of 2 kg moving at 1 m/s. Estimate the order of magnitude of a punch by Mike Tyson. Compare these two orders of magnitude. Why might sunlight cause skin cancer?

Figure 3.7: The names of the dierent sorts of light.

4. Atoms can have electrons in excited states. Electrons in these excited states can, by 34

emitting photons of light, lower their energy from an excited state into their ground state. As the energies of the atomic orbitals are xed, the light emitted have xed frequencies. For the hydrogen atom these xed frequencies typically belong to series, see Figure 3.8. Deduce equations for the frequencies of emitted light for both the Balmer and Lyman series.

Figure 3.8: Light emitted by excited state hydrogen atoms.

5. (a) (10 points) An electron in a Li2+ occupies the 4p atomic orbital. What is the shortest wavelength of light that can be emitted by this ion? (b) (15 points) Light is absorbed by this same ion, causing an electron to y o with speed 1.60 106 m s1 . What is the frequency of this light? (Physical constants which you might need for this problem are given on the bookends of most freshman chemistry textbooks and on the internet.) 35

6. In the previous chapter you were asked to consider the order of magnitude of the kinetic energy of the nucleus and the electrons in an atom at room temperature. What is the ratio of the orders of magnitude of these energies (for a mole of atoms) compared to a punch from Mike Tyson? 7. Draw a graph indicating how the valence atomic orbital diagram of a neutral boron atom changes as a function of the strength of an external magnetic eld. The horizontal axis of this graph should be the external magnetic eld strength. 8. Consider Figure 3.4. For l = 2, there are ve possible ml quantum numbers. Draw a picture like that of Figure 3.4 for these ve quantum states. 9. Consider a two-dimensional world. Angular momemtum is still a conserved quantity, but there are signicant changes in directional angular momentum. Adapt Figure 3.4 for such a 2-D world. Based on the gure you drew, deduce the 2-D law for possible ml quantum numbers as a function of l. What changes would there be in a 2-D worlds periodic table? 10. For the carbon atom, the energies of the 2s, 2p, 3s, 3p and 3d orbitals are approximately -21, -11, -4, -3, and -1 eV. (An eV/molecule corresponds to roughly 100 kJ/mol.) Calculate the energies of light which can be absorbed by a carbon atom up to a maximum energy of -10.5 eV. Are these energies in the ultra-violet, visible, or the infra-red regions of light? Is it possible for diamonds to be colorless? 11. In the photoelectron experiment, a photon of light travels across a chemical sample. For low energy photons not too much happens to the sample. But at a certain photon frequency, the sample ejects one of its electrons. Furthermore for all frequencies above this threshold frequency, electrons continue to be ejected. Calculate the threshold frequency for carbon. The existence of this threshold energy is part of the photoelectron 36

eect. Einstein won the Nobel prize for discovering this eect.

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