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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 ﬁrst-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 ﬁrst year student taking Chemistry 2160, here are some thoughts about what will happen in this course. Things are going to be diﬀerent. While students often feel that Chem 2150 was an extension of AP high school chemistry, the same will not be the case this

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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 ﬁelds are organic (second year chemistry), physical (third year), and inorganic (fourth year). Students who take these upper level chemistry classes can ﬁnd 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 ﬁelds 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 ﬁrst time, in the last year, three former students, who are now in ﬁnance, have come by to talk about this class. All three told me the same thing: they ﬁnd 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 ﬁnancial careers. Whatever your ﬁnal ﬁeld 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

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None of the ideas in this book were originally created by my research group. Kenichi Fukui. Instead at the end of each chapter a few texts or articles are listed which could help enrich your understanding of the given material. Problem sets and old exams will also be given. we will need discuss only two types of chemical bonds: covalent and ionic bonds. and molecular orbital theory. Roald Hoﬀmann. David Pettifor. quantum mechanics. I was taught there were three types of strong chemical bonds: the covalent. So for this course. Such references will be kept at a minimum. I do not propose. the covalent bond is much more diﬃcult to understand. In this book you will learn the quantum mechanical basis of the covalent bond and the electrostatic nature of the ionic bond. giving an accurate scientiﬁc bibliography for each of the subjects covered in this book. the bulk of this course will be devoted to the covalent bond. we can rely on a classical sense of the material world. In this book we will discover that the metallic bond and the covalent bond can be productively treated in a single uniﬁed approach. 3 . I can claim no original credit for anything in this book. the ionic and the metallic. nor am I capable of. The Nature of the Chemical Bond. To understand the covalent bond you will need to learn about the electron. and Klaus R¨ denberg ﬁgure among the many chemists and material scientists whose key u ideas are incorporated in this book. Much of the content of this course is not covered in this landmark book. so as to not overwhelm the student.book (based on lectures given here at Cornell) ﬁfty years ago. For the ionic bond. when I took freshman chemistry. Only in the last 10-15% of this course will we consider ionic forces. the virial theorem. Of the two. Due to the necessary ground-work required for the former subject. To give you some understanding of our ﬂuxional understanding of the chemical bond.

While this book is hopefully a guidebook. every now and then I would ﬁnd a book where I had the sensation the author was trying to explain to me a full subject. The story could have been thermodynamics (Enrico Fermi’s book with this same title). I hope that its intent can be the same. Follow the story as I tell it. you will gain mastery of the subject. 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. The books unfolded like stories. While this book will not come close to the clarity of the classics. but I certainly got every exam question on thermodynamics correct. but challenge the story as well. Before every lecture read ahead the chapter or chapters in the book which the lecture will cover.2 This book is not a textbook As a student in this class. I didn’t do very well in ﬁrst year physics. I would like you the student to get wrapped up in a story. for you to post your questions. Blackboard. My own personal experience was that the textbook approach. which the book and the lectures are trying to express. Textbooks tend to have numerous editions and are based on a collective knowledge of the ﬁeld. or regular polytopes (Coexter’s book). Find out which ideas make sense to you and which do not. When I was a student. I hope to take you out of your comfort zone into places where you will not be familiar. They contain the promise within them. that if you just follow the textbook. If we (the teaching staﬀ and the students together) are successful. Chemical errors in the book noted in Blackboard before 4 . Try to ﬁgure out the chain of logical thought. it is not a textbook. A site will be placed in the Cornell course web site. rarely worked. These books worked for me. Followers do not become masters and teaching-learning is at its core a one-onone activity. the story of the chemical bond. as they understood it to be. the best questions will be awarded 1 or 2 extra credit points. To encourage you to post thought provoking questions.1.

speak up. After the lecture. there will be at least one question which will place two separate concepts of the course into a single explicit problem. In the best of all possible worlds. Please feel free to ask questions in class. On every exam. make up your own problems. but if you ﬁnd the classroom lecture still does not make sense. if you as a student can start thinking of such questions yourself. I will know we. have succeeded as teachers. 5 . I will try to answer the Blackboard questions in class. exams are learning experiences. the teaching staﬀ of this course. review what it is you heard. and what it is you understand. 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 diﬀerent ways.the relevant lecture will also receive 1 point. Exams in this course are my questions to you. Think of how this material relates to other material in the course. (The course total is 500 points). Start doing the problems relevant to the material. If you can.

see Figure 2. The word orbital was originally chosen for its similarity to the word orbit. 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.Chapter 2 The electron To understand the covalent bond. of which you will have seen in high school AP chemistry. electrons move around the nucleus. The planetary analogy for electron motion has many virtues.1 Orbitals Electrons in atoms lie in orbitals. 2. one must understand the electron. We therefore begin our course by stating facts about electrons. and the planet sits in the gravitational potential well of the sun. some. U ∝− mE mS r 6 .1. Even the relation describing electronic and planetary potential energies are the similar. Just as planets move around the sun. but not all.

and r are respectively the charge of the electron. the mass of the sun.1: Planetary vs. while Pluto. In both planetary orbits and electron orbitals. the farthest planet from the sun. has the 7 . the further away a planet is from the sun. and r are respectively the gravitational potential energy. the strength. the mass of the earth. 2m where p is the momentum and m the mass. Mercury has the most negative solar gravitational potential energy. Per kilogram. electronic motion where U. (Classically. Potential energy is the U value given in the equations above. First. the momentum is deﬁned to be p = mv. mE . the charge of the nucleus and the distance between the electron and the nucleus. q+ . the less gravitational potential energy it has. Kinetic energy is p2 . The analogy between orbits and orbitals bears one main strength and one main weakness. where v is the velocity. Analogously.) The Virial Theorem: On a per kilogram basis. mS . the concepts of potential and kinetic energy can be exactly deﬁned. and the distance between the earth and the sun. the potential energy of an electron in the electrostatic well of a nucleus obeys the relation: q− q+ r U∝ where q− .Figure 2.

As the Au 1s orbital lies close to the nucleus.5 × 108 30 8 24 2. the faster the electron moves. For motion like planetary motion.9 × 10 4. Planetary motion obeys the Virial Theorem.3 × 10 7.8 × 109 6. electrons in this orbital move fast: Au 1s orbital electrons move at 0. travels at one tenth Mercury’s speed. electrons move 8 . Table 2. for example.6 times the speed of light.8 × 107 48 1.8 4. The electron orbital closest to the nucleus is called the 1s orbital. but less kinetic energy as well. The closer an electron lies to the nucleus. Pluto therefore not only has a less negative potential energy than Mercury. According to the virial theorem.4 9 5. where the 1s orbital is much farther from the nucleus. The farther a planet is from the sun.8 × 108 13 1. Pluto. Mean Distance from Sun (km) Mean Velocity (km/s) 5. 100 times futher from the sun than Mercury.4 × 109 10 2.1: Planetary Orbital Properties. a theorem which says that there is a ﬁxed relation between potential and kinetic energy.5 × 109 5. In Au. just like planets in stable orbits. In Table 2. the slower it moves. But there is another compelling trend to planetary energies.least negative. the virial theorem states: 2T = −U where T and U are respectively the kinetic and potential energies.1 we list average planetary velocities.1 × 108 35 1. obey the virial theorem. the more negative the potential energy. the more negative is its potential energy. In the hydrogen atom by contrast.7 Planet Mercury Venus Earth Mars Jupiter Saturn Uranus Neptune Pluto Electrons in stable orbitals obey the virial theorem: Electrons in stable orbitals. there are electrons which lie very close to the nucleus.

Electrons do not lie in orbits: The orbit-to-orbital analogy has one major breakdown. electrons in the course of their motion vary their distances from the nucleus. Figure 2. Electrons are best described with quantum mechanics while planets are best described by classical mechanics.2: ﬂy trajectory vs.much slower. where the planets maintain a more or less ﬁxed distance from the sun. ﬂy probability distribution 9 . Rather than thinking of planetary orbits. at only 1 137 times the speed of light. It plays an important role in physics. it has a a name. the Fine Structure Constant. This latter number is so useful.

) The 2p distribution is called ρ2p . Excited state distributions: We can also envision excited state distributions. As the Figure shows. see Figure 2. under the right circumstances. It ﬂies much farther from the plate of food and typically no longer lands on the food plate. Once one disturbs a ﬂy. the electron is never found on the center of the distribution. the electron lies further from the nucleus than an electron in the 1s orbital. like ﬂies. In the 2p orbital. also have excited states.Comparison of electrons to ﬂies: A qualitative picture might be useful here. As the name implies the excited state is a distribution of higher energy than the ground state distribution. stay in these distributions for long periods of 10 . it ﬂies in a much more erratic and energetic manner. for instance by trying to kill it. As the distance from the plate of food increases. Both the 1s and 2p distributions are stable distributions: electrons can. The ﬂy (the electron) in its lowest energy state ﬂies close to the plate of food (the nucleus) and sometimes alights on the plate itself. For historical reasons. For atoms which have just one or two electrons the ground state distribution for the electron is always the 1s distribution. if the electron enters the 2p orbital. This distribution is more or less the least energetic proﬁle of a non-sleeping ﬂy. (One major diﬀerence between an excited ﬂy motion and an excited electron motion is that while the ﬂy always ﬂies faster in its excited state. the electron ﬂies slower. Both ﬂies and electrons can enter excited states. the probability decreases. the most probable place the ﬂy would be located is directly on top of the plate of food. where ρ is the Greek letter rho. A good picture for an electron circling a nucleus might be a houseﬂy circling a plate of food.2. We call the lowest possible energy probability distribution the ground state distribution. In describing the ﬂy’s position it is useful to envision a probability function. Electrons. Just like in the ﬂy excited state. This function gives the relative probability that the electron is located at a given place. one of the most important higher energy states of an electron. the 1s distribution is typically called ρ1s .

1s and 2p electron probability distributions 11 .3: Ground state and excited state ﬂy vs.Figure 2.

for unstable electron orbitals.time. we can further deduce relative total energies. We can similarly compare most pairs of electron probability distributions. once you know integration you will be able to get exact numerical answers). In the former distribution. For example. Thus while in all cases we can deduce the electrostatic potential energy. Electrons in unstable distributions: Unfortunately. in general. For now. Potential energy and electron distributions: From electron distributions we can deduce potential energies. This comparison is important. Recalling the numerical expression for the electrostatic energy. Wavefunctions. the Greek letter psi. As the total energy is the sum of the kinetic and potential energy. knowing just the electron probability distribution alone. In quantum theory. compare the ρ1s and ρ2p distributions shown in Figure 2.3. the virial theorem only applies to stable electron orbitals. we must go beyond the electron probability distribution. while q− (the electron) is a negative number. At this early stage in your technology career. U ∝ q− q+ . Electrons obey quantum mechanics: Electrons obey quantum mechanics. we know nothing either about the kinetic or the total energies. generally denoted by ψ. by applying the virial theorem we know relative kinetic energies. the kinetic energy of an object can be determined by knowing its wavefunction. the electron on the average lies much closer to the nucleus than for the latter distribution. are related to the probability 12 . r and noting that r on the average is smaller for the 1s distribution. while q+ (the nucleus) is a positive number. we ﬁnd the value of U more negative for the 1s state than the 2p state. In such cases. if we know the relative potential energies. you may only be able to deduce qualitative potential energy trends (later.

4: 1s and 2p wave functions and probability distributions 13 .Figure 2.

The waves closest in appearence to the two wavefunctions are shown in Figure 2. Figure 2.5: 1s and 2p wave functions and waves with similar wavelengths Electrons are waves: The wavefunctions ψ1s and ψ2p bear a qualitative similarity to waves. The wavefunctions of the 1s and the 2p orbitals are shown in Figure 2.density by the relation: ρ ∝ ψ2. 14 .5.4.

2. λ1s is shorter than λ2p . They both therefore obey the virial theorem. where λ is the Greek letter lambda. In quantum mechanics there is a ﬁxed relation between λ and kinetic energy. 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. λ2 Tnon−rel ∝ 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. We call these wavelengths λ1s and λ2p .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.Let us consider the two waves shown in this Figure. For the 1s and 2p orbitals. The results we obtain about planetary orbits orbits proves relevant to stable atomic orbitals. For particles moving at or close to the speed of light Trel ∝ 1 λ while for particles moving signiﬁcantly slower than the speed of light 1 . Both waves have a wavelength.) The electrons vital to chemistry lie far away from the nucleus and hence have slow speeds. speeds signiﬁcantly less than the speed of light. We begin with orbits. 15 . In chemistry the latter equation is therefore much more important. Both the 1s and 2p orbitals are stable electron states. By the equation above. the 1s state therefore has more kinetic energy.

the length of this same arrow is proportional to the speed of the planetary motion at the same given time. the length of the arrow L is proportional to the length of r times the length of v. L. v. is an arrow describing the direction of motion of the planet. describes the arrow pointing from the sun to the planet. (The direction of the arrow v gives the direction of travel at a given time. velocity.Figure 2. These relations are expressed by the formula L = mr × v. r. r. The velocity vector. the velocity vector.6: The position. 16 . As the Figure shows. vectors Planetary picture of angular momentum: In Figure 2. v. where the position vector. The position vector. Furthermore. and angular momentum. r. v.6 we re-illustrate planetary motion. and the angular momentum vector. if r and v are mutually perpendicular. L. where m is the mass of the planet and × is the vector cross product. angular momentum can be represented by an arrow which is simultaneously perpendicular to both r and v.) Angular momentum is also a vector. have been added on.

We leave this task to the student. If not. Conversely the greater the value of L. we note here the principal ﬁnding for orbitals: for all atoms and ions with more than a single electron to them. In outer space. the greater the value of L. This result is absolutely true for planetary orbits. We note the chief ﬁnding of such a calculation: the farther a planet lies from the sun. As our primary interest is electrons in orbitals. We conclude. In Table 2. the less negative is the value of the total energy.Relation between angular momentum and stable orbitals: The angular momentum is therefore completely determined by knowledge of r and v. 2. A million miles from this single proton is a single electron travelling at one-thousanth the speed of light. the greater is its angular momentum. For an atom with an electron. Based on the virial theorem prove or disprove the following statement. why not. From the virial theorem. the greater the value of r. 3. increases in the angular momentum lead to less negative total energies. the total energy of the electron can never be positive. we can deduce the angular momentum for one kg of any of the listed planets. Applying the formula above to the values in this Table.3 Problems 1. the less negative is the potential energy. (One of the problems at the end of this chapter asks the student to conﬁrm that this fact is a consequence of the virial theorem. 2. we know the greater the value of r. U. and the less the value of the kinetic energy. L.1 we listed the magnitudes of r and v for the nine planets. the greater the angular momentum. One curious feature of the ρ1s and ρ2p probability distributions is that at distance r = 0 17 .) Applying the virial theorem to angular momentum: In summary. Does this situation prove that the virial theorem is sometimes false. there is a single proton. the greater the value of r.

18 . At room temperature a nucleus has roughly two and a half kJ (kiloJoules) of kinetic energy per mole. 4. to one signiﬁcant ﬁgure what is the conversion factor between miles per hour and meters per second? 7.. The gravitational constant is G. Show why the values of the angular momentum cause ρ2p to be equal to zero at r = 0. 5. 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. ie. even higher energy state) than the 2p state is the 3d state. 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. Angular momentum is a conserved quantity. What is the order of magnitude of the ratio of the kinetic energy for the electrons vs. Deduce from this fact that all planetary motion is planar. The next more excited state (ie. Compare an adult man walking at 3 miles an hour. Draw two fundamentally diﬀerent possible qualitative pictures of both ψ3d and ρ3d . a baseball thrown at 50 miles per hour and a bullet travelling at 1000 m/s. Both linear momentum and energy are functions of the mass and velocity. Write an expression for the angular r momentum of this planet using only the variables M. Electrons are travelling at one one-hundreths to one-tenth the speed of light. Estimate the kinetic energy and the momentum of these three without looking up any information on the internet. For the sake of comparison draw on the same page ψ2p and ρ2p .. 6. and r and the constant G. Which has the greatest momentum and which has the greatest kinetic energy? Without looking up any information on the internet.the former function has a non-zero value while the latter function is exactly zero. An atom is composed of a nucleus and its electrons. U = −G mM . m.

In what way are the results of the previous two problems in contradiction with this fact? 19 . v. What is the ratio of the kinetic energies of the sun and the planet? What variables control this ratio? 10. Express R as a function of m. M and the speed of the planet. 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.9. Using the law of the conservation of linear momentum. write an expression for the speed of the sun. 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. Assume the center of mass is motionless. the center of mass. M. and the sun lie at all times in a straight line. the kinetic energy of the nucleus is halved. Let r and R be respectively the distances the planet and the sun are from their center of mass. If the absolute temperature is halved. Further assume that the planet. as a function of just m. V . Are your calculated values of these two ratios compatible with this assumption? 11. but the kinetic energy of the electrons remain essentially the same. and r.

All quantum numbers are unitless. Quantum numbers: All electrons in atoms lie in an orbital. the student. a wave function. however. In this chapter we will give as plain a rendering of these facts as possible. All stable atomic orbitals can be described by four diﬀerent quantum numbers. 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. A quantum number is a kind of physical constant. (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 ﬁrst time to understand the organization of the periodic table (these facts are therefore important to chemistry as a whole). 20 . Such orbitals are called atomic orbitals. to make much sense of them. The facts themselves are so peculiar that I worry that it will be hard for you.Chapter 3 Electron orbitals and the periodic table In this chapter we will make a number of striking statements about electron orbitals. They are.

and so forth) while RH = 2. n2 where Z is the nuclear charge (Z = 1 for H. To distinguish these constants from the ﬁxed constants (such as the speed of light).) the relation between the principal quantum number and the total energy is a precise one: En = −ZRH . As long as an electron in an orbital with assigned quantum numbers is unperturbed neither by other atoms nor receives nor emits light. Li2+ . Of all the quantum numbers. the quantum numbers of the electron stay ﬁxed. The lowest possible value for n is 1. While for atoms with more than one electron. Quantum numbers are conserved quantities. scientists call these latter constants conserved quantities. For atoms and ions with just a single electron (H. the principal quantum number. He+ . For all atoms and all ions there is at least one atomic orbital for each value of n. it is the principal quantum number which gives the most information about the energy of the orbital. But scientists speak of another kind of constant.When scientists speak of constants they have two diﬀerent constants in mind. The principal quantum number is always a positive whole number. In unperturbed collections of physical objects (such collections are called systems) quantities such as the total energy or the total momentum do not change. etc.2 × 10−18 J. 21 . the relation describing the total energy is a more complicated one. are constant only so long as the system is unperturbed. These are constant numbers: neither the speed of light nor the rest mass of an electron ever changes. On the one hand there are constants like the speed of light or the rest mass of the electron. n remains a dominant energetic variable. Principal quantum number: The ﬁrst quantum number is n. These latter constants. 2 for He.

3.1 Orbital angular momentum Orbital angular momentum quantum number: The orbital angular momentum quantum number. is a whole number which ranges in value from 0 to n − 1. The relation between l and L: In the case of the principal quantum number. l. and l = 2 are d orbitals. l. and for an n value of 3.6 × 10−31 kJ · s. From the text above. the 2p orbital refers an orbital where n = 2 and l = 1. where n is the principal quantum number. ¯ where h is Planck’s constant divided by 2π and where L = |L|. The units of Planck’s constant are of interest. Its value is: h = 6. Thus for an n value of 1. For example. n. if one divides h by 2π one obtains h. one can write an exact equation relating total energy to n. The l quantum number is suﬃciently important in chemistry that each of the values of l have speciﬁc names. the only possible value of l is l = 0. the angular momentum. for an n value of 2. We derive these units by examining the equation relating L2 and l. l = 1 or l = 2. the total orbital angual momentum is exactly determined for all atoms and ions. The 3s orbital refers to n = 3 and l = 0. l = 0 or l = 1. l = 1 are p orbitals. we have the sense that the principal quantum number tells us something about the energy of an electron. Chemists typically designate orbitals by a combination of the principal and orbital angular momentum quantum numbers. l = 0 orbitals are called s orbitals. As l is unitless and L2 is in units of angular 22 . only for atoms or ions with exactly one electron. h = ¯ ¯ 1 × 10−31 kJ · s. ¯ Planck’s constant: Planck’s constant is one of the most important constants in physical chemistry. The formula relating l to L is L2 = h2 l(l + 1). For the case of the orbital angular momentum quantum number. l = 0. The orbital angular momentum quatum number tells us about another physical quantity.

for all atoms with more than one electron. the equation L2 = h2 l(l + 1) tells us that h is in units of angular ¯ ¯ momentum. Relating l to the total energy: The greater the value of l. For planets in stable orbits (see the Appendix of the previous chapter). To make this connection. Planck’s constant will give us the order of magnitude of many of the basic angular momentums found in chemistry. Thus. the greater is the total energy. We now make the connection between L and the total energy. Figure 3. the greater the value of L. Thus the 2p orbital has a less negative total energy ( a less negative energy is a greater energy) than the 23 . the greater the value of L. we invoke the similarity between electron orbitals and planetary orbits. the greater the value of L. the greater the value of l. but with one proviso: the atom or ion in question must have more than one electron. This statement is also true for atoms. As we shall see later.momentum squared. the greater is the value of E.1: The relation between E and l for several diﬀerent atoms.E. and the greater the value of L.

Summary of the relation between n.1. E is solely a function of n and l. For a ﬁxed value of l. E. the less negative is the total energy. for atoms and ions with more than a single electron. for a ﬁxed value of n. the total energy. Examples of these trends are shown in Figure 3. the greater the value of l. for atoms and ions with just a single electron to them.2s orbital. 24 . Figure 3. the greater the total energy. the total energy. is independent of l and depends solely on n: the greater the value of n.2: A schematic for the Aufbau principle. the greater the value of n. similarly. In the absence in a magnetic ﬁeld. the greater is the total energy. similarly the 3d has higher energy than 3p which is higher in energy than 3s. l and the total energy: In the absence of a magnetic ﬁeld.

or 1. ml is always a conserved quantity.2 Directional orbital angular momentum The third quantum number is the directional orbital angular momentum. ml is a conserved quantity: In the absence of any magnetic ﬁeld. etc. L = 2¯ . The value of ml is restricted to being the integers which range from −l to l in value.The ordering of the atomic orbitals: The ordering of the energy of atomic orbitals follows a straight-forward mnemonic. the lowest energy orbital is 1s. but here unspeciﬁed. and the ml = 0 state refers to a speciﬁc. or 1. We enumerate here the L which correspond to the quantum numbers ml = −1. the ml quantum number remains conserved. − 2¯ ). Thus for all s orbitals. 3p. 3d. The magnitude of L is ﬁxed by the formula √ L2 = h2 l(l + 1): for l = 1. see Figure 3. where l = 0. 3. 0. ml can have one of three values: -1. 4s. While the l quantum number determines the magnitude of the angular momentum. ml = −1 to L = (0. 0. Origin of ml : The ml quantum number is derived from the vector nature of the angular momentum. it tells us nothing of the direction of the angular momentum. However. ml can furthermore remain a conserved quantity if the external magnetic ﬁeld is aligned in an appropriate direction. in the previous example of p orbitals. 2p. 3s.2. The most illuminating example are the p orbitals. if the magnetic ﬁeld is aligned in the z direction. where l = 1. 0. where l = 1. whose ml were given with respect to the z axis. The energies of the orbitals then follow in the sequence 2s. 0. the direction of L changes: ml = 1 corre¯ h √ √ h h sponds to L = (0. ml = 0. while for p orbitals. For example. As the Figure shows. vector perpendicular to the previous two vectors. 25 . For all atoms with more than one electron.2. ml . the energies of the orbitals follow a sequential pattern most easily discerned with the diagonal lines of Figure 3. 2¯ ).

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 .4: Three possible orientations for an l = 1 electron. the ml = −1 is highest in energy. B. Referring again to the previous example where l = 1 and the magnetic ﬁeld is aligned along the +z axis.Figure 3. 0−1 as a function of the external magnetic ﬁeld strength. The relation between ml and the energy: The quantum number ml aﬀects the total energy only in the presence of an external magnetic ﬁeld. Figure 3. the ml = 1 state is lowest in energy.3: The energies of ml = 1.

We consider now just the case where the charged particle has an angular momentum parallel to the direction of the magnetic ﬁeld. we can consider the 27 . where we could further consider directional orbital angular momentum. 0. L). is half-integral in value. the value of S for an electron √ is also always ﬁxed at 3¯ /2. 3. The relation between s and the spin angular momentum. In such a case. As Figure 3.the ml = 1. We can imagine three such cases: the charge has an angular momentum parallel. S is the same as is found between l and L: S 2 = h2 s(s + 1). L = (0. L) as is found in the ml = 1 state. we place into the z direction. an electron always has an internal angular momentum called its spin.3 Directional spin quantum number Electron spin quantum number Independent of an electron’s spatial orbital. −1 states are plotted as a function of the strength of the magnetic ﬁeld. Directional spin quantum number: Just as in the case of of orbital angular momentum. 0. the quantum mechanical electron behaves in exactly the same way.4. In a classical picture the energy of such a charged particle would lowered by the magnetic ﬁeld. Similar arguments can be applied to the ml = 0 and −1 orbitals.3 shows. ¯ As the s quantum number is always ﬁxed to the value of 1/2. We now turn to the electron with the angular momentum (0. S and s both being ﬁxed. This angular momentum carries the spin quantum number s = 1/2. perpendicular and anti-parallel to the direction of the magnetic ﬁeld (which for convenience. These results can be understood by thinking of a classical charge moving in a ﬁxed circular orbit. 0. The spin quantum number while unitless. just as in the classical picture. chemists rarely concern themselves h with this quantum number. see Figure 3.

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. The number of atomic orbitals with the same value of n and l: In the absence of a magnetic ﬁeld. Take for example the 2p or the 3p states. While ml and ms do specify the direction of the orbital and spin angular momenta.directional spin quantum number. the student will need to learn some additional facts about quantum mechanics. 0. 28 . for chemists. 0. The value ms = 1/2 corresponds to the S = (0. A d orbital. and ms ) specify completely a stable atomic orbital. In both cases l = 1 and ml ranges over the values of 1.4 Electron orbitals and the periodic table The four quantum numbers (n. the ms quantum number is limited by s. the quantum number ms has two possible values −1/2 and +1/2. ml . that to learn about the important role these numbers play in chemistry. It may not be suprising therefore. ms has the value 1/2 or -1/2. 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. with l = 2 has simulanteously both one of ﬁve possible values for ml and one of the two possible values of ms : a total of ten possibilities. Recalling that √ √ h the magnitude of S is 3¯ /2. neither ml nor ms play any role in either the total angular momentum or the total energy of an electron. l. 3¯ /2) and h the value ms = −1/2 corresponds to a vector pointing in the opposite direction. ms can range in values from −ms to +ms . As in our case s = 1/2. 3. These numbers are called quantum numbers as they relate to the quantum mechanical properties of electrons. ms . where values of ms must diﬀer from each other by whole numbers. or -1. In just the same way that the ml quantum number is limited by l.

lie in diﬀerent orbitals: once they come together in an atom. We can combine this ordering with the Pauli exclusion principle. ie. helium. it is none-the-less impossible to distinguish electron A from electron B. (By contrast. 29 . The next lowest orbital is 2p. a group of electrons are identical to one another.Identical particles: In quantum mechanics.) The Aufbau principle: In Figure 3. Consider two electrons (let’s call then A and B) and even let these two electrons have diﬀerent quantum numbers. Fermions with a given set of quantum numbers exclude all other identical particles from the state which they occupy. bosons draw other identical bosons into the same orbital: lasers. we gave the energy ordering of the various atomic orbitals. 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. Consider now an atom with 10 electrons. these two electrons will occupy the lowest energy orbitals. One of the two electrons has ms = 1/2. the other has ms = −1/2. Fermions obey the Pauli exclusion principle: only one electron can have one complete set of four quantum numbers at a given time. He has two electrons in the 1s orbital. The atom Ne. and 2p states ﬁlled. with ten electrons has all 1s. 2s. As the arguments above demonstrate. neon. Thus there can be six electrons in the 2p state. superconductors and superﬂuids are all examples of boson attraction. The atom with two electrons is He. In this orbital ml can take one of three values and ms on of two values: a total of six possibilities. Two electrons can occupy the 1s orbital. where s = 1 is a boson). In a stable arrangement of the atom. Consider for example an atom with two electrons. All particles which have this sort of property are called identical particles.2.. 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 diﬀerent orbitals. 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 two lowest orbitals are 1s and 2s.

Note in the AO diagram. Chemists represent these occupations in a number of diﬀerent ways. We illustrate two of the most important diﬀerent ways here. we list a series of occupied and unoccupied atomic orbitals. with nine electrons is 1s2 2s2 2p5 .5: Three possible AO diagrams for the ﬂuorine atom. list a portion of all the occupied and unoccupied atomic orbitals. For example for Ne the sequential ordering is 1s2 2s2 2p6 . where the superscripts indicate the number of electrons occupying a given orbital. It is not necce30 . Three examples of the F AO diagram are shown in Figure 3. Atomic orbital diagrams: Even more important for this course are atomic orbital diagrams.5.Electron conﬁgurations: The electron orbital occupations play a dominant role in the chemistry of the elements. The ﬁrst method is to list the occupied orbitals in sequential order. Atomic orbital diagrams. while F. Figure 3. AOs. The picture on the right is the valence atomic orbital diagram. ﬂuorine.

The nomenclature of valence orbitals is somewhat vague. Ar (Ar has 18 electrons). Thus is the case of Fe. we show just the valence atomic orbitals. Fe.5a. Chemists further diﬀerentiate orbitals which lie above the last ﬁlled noble gas conﬁguration into one of two types. We speak more of this third example in the next two paragraphs. However.sary to list all the occupied and unoccupied orbitals.5b. just the valence and some of the excited-state atomic orbitals were given. Chemists will therefore write the Fe electron conﬁguration as [Ar] 4s2 3d6 . The lowest energy of these orbitals are called valence orbitals. in Figure 3. The third example shown is the most commonly used. In the case of Fe. with 26 electrons. In Figure 3. Chemists call the orbitals ﬁlled up to the last ﬁlled noble gas conﬁguration core orbitals. core and excited-state orbitals: The electron conﬁguration notation listed above becomes quite cumbersome for atoms with a large number of electrons. the valence orbitals are those orbitals which come between the last ﬁlled noble gas conﬁguration and the next not-completely-ﬁlled noble gas conﬁguration. valence orbitals are sometimes ﬁlled. and 4p orbitals. If we were to represent its full electron conﬁguration it would be 1s2 2s2 2p6 3s2 3p6 4s2 3d6 . valence and some of the excited state atomic orbitals were shown. valence orbitals could be taken to be the 4s. core orbitals are always ﬁlled. Orbitals which lie above both the core and valence orbitals are called excited state orbitals. Valence. and excited-state orbitals are never ﬁlled. and ﬁnally in Figure 3.5c. This ﬁnal diagram is the valence atomic orbital diagram. In a stable arrangement of an atom. as a good rule-ofthumb. Chemists often will abbreviate this series by stating explicitly only those orbitals occupied after the last preceding noble gas element. Consider iron. the last noble gas conﬁguration ﬁlled is argon. the core. 3d. 31 .

6 we present a periodic table based on the consecutive ﬁlling of atomic orbitals. and so forth. The number of elements for each value of n and l depends on the number of possible diﬀerent values of ml and ms .Figure 3. 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. We conclude this chapter by 32 . We are now poised to understand the shape of the periodic table. In Figure 3. then the quantum numbers play a role in the periodic structure of the elements. The periodic table: All chemistry students in this course have seen the periodic table. with short rows at the top and long rows on the bottom. 3. then the 2s. As a student you may have wondered at its unusual format. and if the counting principle developed for these four quantum numbers is correct.6: The relation between the periodic table and the Aufbau principle. First ﬁlled is the 1s orbital.5 Conclusions This chapter has demonstrated that if all atoms have four quantum numbers.

including the 1s 2s. Si. In this column. Label axes and state numerically the actual 33 . We conclude that it is the l quantum numbers which play the greatest role in periodic trends. the valence orbitals all have diﬀerent n quantum numbers. We deduce the number of occupied s and p orbitals is important. 3. 3s. 2p. 3s. draw a qualitative Atomic Orbital diagram of iron. We further conclude that the ml and ms quantum numbers also play a role in atomic properites. examine column 14 of the periodic table. Based on the Aufbau principle. From previous chemistry courses.C. and Ge exactly two of the six possible valence p orbitals (and all the valence s orbitals) have been occupied. Giving a spatial shape to each of these orbitals will allow us ﬁrst to make the bridge from quantum numbers to the shape of orbitals. 3d and 4s orbitals.6. but the same l quantum numbers. 3p.examining this proposition more fully. Examining Figure 3. Draw a quantitatively accurate atomic orbital energy diagram for Li2+ . 2. For example. And if this is so. 3d. 4s and 4p orbitals in your picture. In the case of the chemically similar C. and ﬁnally understand the relation between the shape of molecules and chemical reactivity. and germanium. the elements carbon. while the n quantutm number is of less importance. Si. we consider an explicit spatial represention of these ml and ms combinations. 2p. it is reasonable to assume that each of occupied valence p orbitals are based on the same combination of ml and ms states. we see that for each of these three elements. Ge lie one beneath the other and all have similar chemical properties. In the next chapter. 3p. second determine the connection between the shape of orbitals and the shape of stable molecules.6 Problems 1. silicon. you have learned that elements lying in the same column of the periodic table often have similar chemical properties. Include the 1s 2s.

Does Li2+ obey the Aufbau principle as stated in Figure 3. ν is related to the energy of one photon of light by the formula E = hν. respectively λ and c by the formula c = λν. The frequency of this light.1.7. Estimate the order of magnitude of a punch by Mike Tyson. by 34 . see Figure 3. Atoms can have electrons in excited states.energies of the orbitals. Calculate the order of magnitude of energy of one mole of photons of low energy ultra-violet light. Why might sunlight cause skin cancer? Figure 3. Compare this diagram to the diagram of neutral lithium. see Figure 3. The frequency of light is also related to the wavelength and speed of the light.2 ? 3. Electrons in these excited states can. 4. Monochromatic light has a ﬁxed frequency. A Joule is the kinetic energy of 2 kg moving at 1 m/s. Compare these two orders of magnitude.7: The names of the diﬀerent sorts of light.

For the hydrogen atom these ﬁxed frequencies typically belong to series.) 35 .emitting photons of light. 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. What is the shortest wavelength of light that can be emitted by this ion? (b) (15 points) Light is absorbed by this same ion. As the energies of the atomic orbitals are ﬁxed. Figure 3.8. (a) (10 points) An electron in a Li2+ occupies the 4p atomic orbital. 5. causing an electron to ﬂy oﬀ with speed 1. the light emitted have ﬁxed frequencies.60 × 106 m s−1 . see Figure 3.8: Light emitted by excited state hydrogen atoms. Deduce equations for the frequencies of emitted light for both the Balmer and Lyman series. lower their energy from an excited state into their ground state.

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. Are these energies in the ultra-violet.4 for such a 2-D world. -11. 9. a photon of light travels across a chemical sample. (An eV/molecule corresponds to roughly 100 kJ/mol.6. 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 ﬁeld. Angular momemtum is still a conserved quantity. there are ﬁve possible ml quantum numbers. For low energy photons not too much happens to the sample. For l = 2. 3p and 3d orbitals are approximately -21. the sample ejects one of its electrons. visible. Based on the ﬁgure you drew. -4. Consider Figure 3. -3. Draw a picture like that of Figure 3. Consider a two-dimensional world. 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. The horizontal axis of this graph should be the external magnetic ﬁeld strength. but there are signiﬁcant changes in directional angular momentum. 8. 3s. In the photoelectron experiment. or the infra-red regions of light? Is it possible for diamonds to be colorless? 11. and -1 eV. What changes would there be in a 2-D world’s periodic table? 10.4 for these ﬁve quantum states. Adapt Figure 3. For the carbon atom. the energies of the 2s. Calculate the threshold frequency for carbon.5 eV. Furthermore for all frequencies above this threshold frequency. deduce the 2-D law for possible ml quantum numbers as a function of l.4. electrons continue to be ejected. The existence of this threshold energy is part of the photoelectron 36 . 2p. But at a certain photon frequency.) Calculate the energies of light which can be absorbed by a carbon atom up to a maximum energy of -10.

eﬀect. 37 . Einstein won the Nobel prize for discovering this eﬀect.

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