SOLID STATE S.O. PILLAI am } Ls . A) a ‘ 5 i . i NEW AGE INTERNATIONAL PUBLISHERS * SE een2 PUBLISHING FOR ONE WORLD NEW AGE INTERNATIONAL (P) LIMITED, PUBLISHERS formerly Wiley Easton Limited) New Delhi Bangalore * Chennai » Guwahati - Hyderabad Jalandhar + Kolkata + Lucknow + Mumbat + Ranchi Visit us at www.newagepublishers.com Copyright © 2005, 2002, New Age International (P) Ltd., Publishers Published by New Age International (P) Ltd., Publishers Fifth Edition : 2002 Sixth Edition : 2005 Reprint : 2005 All rights reserved. No part of this book may be reproduced in any form, by photostat, microfilm, xerography, or any other means, or incorporated into any information retrieval system, electronic or mechanical, without the written permission of the copyright owner. ISBN: 81-224-1682-9 Rs. 325.00 2345678910 C-05-08-330 ‘Typesetter : Print Tex India. Printed in India at Mehra Offset, New Delhi. PUBLISHING FOR ONE WORLD NEW AGE INTERNATIONAL (P) LIMITED, PUBLISHERS. (formerly Wty Eastern Linited) 4835/24, Ansari Road, Daryaganj, New Delhi - 110002 Visit us at www.newagepublishers.comCONTENTS Preface to the Sixth Edition Preface to First Edition A ements An academic experience with Prof. A.P.J. Abdul Kalam Some Views... 1.__INTRODUCTION 2.___ REVIEW OF ATOMIC STRUCTURE : ‘The Rutherford Model of the Atom Conclusion of Rutherford’s Theory Drawbacks of Rutherford Model of the Atom Bohr Madel of Atom Bohr’s Theory of Hydrogen Atom Total of the Electron in the. Orbits Calculation of r, and E, for Hydrogen Atom Bohr’s ion of Hy Spectral Series of Hydrogen Shortcomings of Bohr's Theory Saaaueaiae ; i Elliptical Orbits for Hydrogen Atom Total of an Electron in an Elliptical Orbit Fine Structure of H, Line Drawhacks of Bohr-Sommerfeld Atom Mode} Vector Aton Model istic. Numbers Pauli's Exclusion Principle Application of Pauli’s Exclusion Principle Electron Configuration Wave-Mechanical Concept of the Atom 3.__INTERATOMIC FORCES AND BONDING IN SOLIDS L + Introduction IL___: _ Force Between Atoms BERREEERHBEE Rx REE eKRe EH BRB BBEBEBRERBBBEGGR Beato ee eweBREERGRE RBH xEEBE Kee i Bee g ERERKRBeH BSSR S SBSBSBBSBR RRERERRERPBBBRAREBS BRERBEBE Copyrighted materialaana shanad 4 gesaa errr G-saeassda Copyrighted materialxviii + Physical Significance of the Wave Function y : Limitations on y and Normalisation of Wave Function BRE i + The Quantum Mecasis of Simple Problens i. £ ERER BER BRESSEEEEEBE E BEBE BREE E ERR EEEREE Schottky Effect "Magnetism in Metals + ANote on Selection of Electrical Engineering, Ma ; : Copyrighted materiala aaddaaa Q4A ad SSSR RN SSSRa eRe aS ga9 98ea i E ] Fk ' yal yas R He 3 Li 2 5 a8: ECE Sata gs i paca 2 sae3 baage: ide Hilal a iP ale Hi au A i agelel @-seanndguxneheudsdaudhs ae i B= a Copyrighted material4B RReeRES * a E Electric Current in Atoms — Bohr Magneton Electron Spin and Magnetic Moment Magnetic Moment Due to Nuclear Spin More about the origin of Magnetism Theory of magnetism in Electrons Diamagnetism Paramagnetism Weiss Theory of Paramagnetism Paramagnetic Susceptibility of a Solid Substances Quantum Theory of Paramagnetism Cooling by Adiabatic Demagnetization Determination of Susceptibilities of Para and Diamagnetic Materials Hund Rules Summary Ferromagnetism ‘Spontaneous Magnetization in Ferromagnetism Materials Quantum Theory of Ferromagnetism Weiss Molecular Field Behaviour of Materials For TS.6,- Curie-Weiss Law) ‘Temperature Dependence of Spontaneous Magnetism ‘The Internal Field And Exchange Interaction Ferromagnetic Domains ‘The Domain Model Domain Theory Experimental Demonstration of the Domain Structure Explanation of Hysteresis Antiferromagnetism Ferrimagnetism (Ferrites) Structure of Ferrites Magnetic Materials 10,__PHYSICS OF SEMICONDUCTORS 1____Introduction U_______The Band Structure of Semiconductors I__:_ Semiconductors SRSSERERBSSES aRS ui BERBER BESERBRESEBEE BR&3SBREN HS SERRE RnR EEK KE 11, DIELECTRICS SYRKae REE ae cea H Mobility of Current Carriers General Study of Excess Carrier Movement Hall Effect Advantages of Semiconductor Devices ‘The p-n Junction ‘The Potential Barrier at The p-n Junction Width of Depletion Layer of The p-n Junction ‘Volt-Ampere Characteristics of The p-n Junction Application of Voltage Across A p-n Junction Rectifier Equation Continuity Equation ‘Some Special p-n Junction Diodes AND RELATED PROPERTIES Introduction apiece Langevin’s Theory of Polarisation in Polar Dielectrics Imernal~Field or Local Field in Liquids and Solids psceciiarads mcr The Static Dielectric Constants of Solids and Liquids a 2 ieee es Properties of Dielectrics in Alternating Fields ‘The Complex Dielectric Constant and Dielectric Loss Dielectrics in Alternating Fields ‘Complex Dielectric Constant of Non-Polar Solids Dipolar Relaxation Absorption of Energy and Dielectric Losses 9 g é BERREBBEBREBE & BRE& BESESE 2 s 3 RERRRBSES 333 aaaxxii Contents XVI Effects of Dielectrics xvi I uirements of Good Insulating Materials xvu Some Insulating Materials 12,__OPTICAL PROPERTIES OF SOLIDS 1 + Introduction U Classical Model — Drude Model m Tonic Conduction wv Optical Refractive Index and Relative Dielectric Constant v ‘Optical Absorption in Metals, Insulators and Semiconductors Mi Colour Centres vu Excitons vi Liminescence Ix Maser and Laser x Lasers xt Application of Lasers xi Physics of Optical Fibres 13, MISCELI ANEOUS TOPICS I Insulating Materials and Their Properties u :__Composite Materials 14.__SOME USEFUL INFORMATION I A Tables I Metric Prefixes M___: Derived $1 Units haviny Names and S; Vv :__ Advantages of $I Units v :__ Some common Differentials and Integrals Appendices Answers to Objective Questions Answers to Problems es Index RERREBEE BEERS BBS 3 z BESRER RE B aCHAPTER 1 INTRODUCTION Ever since Adam and Eve felt a need for some sort of apparel in the Garden of Eden, mankind has been concemed with problems of materials. While Adam and Eve and their immediate descendants had only rel- atively simple materials problems such as clothing and the construction of shelter, we in our modern civili- zation have far more numerous problems. We stil! have the age-old needs for clothing and shelter, but in our modern life, we have become extremely dependent of a great variety of materials. In fact, materials provide the framework plus the sinews and ligaments that hold our civilization together. As a small example, con- sider the Boeing 747 “Jumbo Jet’ which serves as part of the intemational transportation system. This air- craft is approximately 1% fibre glass, 4% titanium, 13% steel, and 82% aluminium. FFor several centuries the few metals and alloys (such as iron, copper, tin and brass), the few ceramics (such as pottery), and the natural polymers (such as wool, cotton, asbestos, and cellulose) were sufficient to meet most human needs. The new age of materials took its birth in the late nineteenth and early twentieth centuries. Imperceptibie progress had been made for centuries, but now new materials are being developed ata rate hitherto unachieved. The tremendous increase in the number of materials available and their varying physical properties, coupled with demands from new applications and more severe service requirements, have brought about many changes in attitudes and view points. Advances in fundamental science have led to the development of anew technical area which we might call a unified science and technology of materials. The range of materials and their properties to the engineer today is vast. The traditional materials like glass, rubber, timber, copper and germanium, are all used by engineers today also, but in character and Properties they are completely different from the past ones. Within one group of materials, properties may range from a soft and easily deformed metal such as lead to tool steels which are hard and tough. Every engineer is concerned with materials and be has to select the most suitable material for the job in hand, be it for civil engineering structure, or a power plant, or perhaps for an electronic component. ‘There is one thing which all materials have in common, and that is they are all composed of atoms. ‘The atoms themselves may differ from one another, but the atoms of all the known elements are composed of the same three kinds of basic particles, the proton, the neutron and the electron. The nature and final properties of the bulk engineering materials we use every day involve the atomic and molecular structure, the degree of order and perfection in these structures, and the forces and energies associated with them. Recent developments in materials science lead towards a new understanding of the nature of materials and suggest a more basic approach to their application. Techniques are available for describing the properties of existing materials and are becoming available for predicting properties of new materials, in terms of their atomic and molecular structures. The behavioural response to fabrication methods and environments can also be related to these factors. Consequently, an understanding of the fundamentals of materials technology is becoming a prerequisite to their engineering applications.2 Solid State Physics ‘Atoms are made up of three types of elementary particies. These are the proton, the neutron and the electron, The proton is a particle which has a positive electrical charge and a mass of 1.67210 kg. The neutron has an almost identical mass (1.675 x 10™” kg), but has no electrical charge. The third particle, the electron, has an electrical charge which is equal and oppocite to that of proton but has a mass only 1/1836 of that of the proton. The atom as a whole is electrically neutral since it contains protons and electrons in equal umber. The number of neutrons in the atom is often the same as, or greater than, the number of protons. Each of the hundred and odd known elements is characterised by a different number of protons in the nucleus. The number of protons contained in the nucleus is termed the atomic number, Z. In an electrically neutral atom, there must be equal number of electrons. The nucleus is normally composed of the two kind of particles: protons and neutrons, and they make up the mass of the atom. The atomic mass number, of atomic weight, M,, indicates the total numbers of protons and neutrons in the nucleus for the simplest atom, hydro- gen: Z= 1,M, = 1, so that the nucleus has just one proton. For oxygen, Z = 8, M, = 16, so that the nucleus contains 8 protons and 8 neutrons. The quoted atomic weights of atoms are not all whole numbers. The atomic weight of hydrogen is 1.008. If M, represents the atomic weight of an element, M, gm of the element is called one gram atomic weight (at. wt.) and Af, kg is 1 kg at. wt. It follows from Avogadro's hypothesis that 1 kg at. wt. samples of all elements have the same number of atoms, now known to be 6.0225 10". This is called Avogadro's number and represented by N,; N, molecules of a gaseous substance constitute 1 kg mol of the substance, ‘The solid state of matter is quite different from either the gaseous or the liquid state, mainly because the atomic particles are packed closely together in some orderly three-dimensional network in space. The kinetic energies are lowered to the extent that movements are restricted to regular vibrations about fixed ‘mean positions and diffusion rates are extremely slow. Nevertheless, diffusion processes in solid materials are of great significance since many engineering phenomens depend upon the rates of diffusion of the vari- ous atoms within the metal. Many electrical engineering materials are solids, and since all solids are made of up atoms, molecules, or other atomic particles, the study of solid state must logically begin at the level of atomic structure.CHAPTER 2 REVIEW OF ATOMIC STRUCTURE 1. THE RUTHERFORD MODEL OF THE ATOM The first exploration of the structure of the atom was made by Rutherford in 1911 making use of a-particles. He bombarded a thin gold foil with a-particies (helium nuclei, which are positively charged particles with an atomic mass number of 4) and found that very many ct-particles passed through the gold foil without being deflected, but some of them were deflected through large angle. The inference was that much of the atom was void space allowing most of the a-particles to pass straight through, but with some particles being deflected owing to their passing close to, or colliding with, a central mass (nucleus) of very small dimensions. The effective diameter of the gold atom is 0.3 nm and the diameter of the nucleus is about 1/10,000 of this size. The first postulation about electrons was that they are in orbit around the central nucieus just as plan- ets round the sun. To incorporate these findings and the discovery of the electron, Rutherford proposed the following model of the atom: This postulates a tiny, massive, and positively charged nucleus around which orbit the negative elec- ‘ons. In Fig. 2.1, an electron is revolving in a circular orbit of radius, r, with a constant velocity, v. The system is now subjected to two forces. Acting inwards will be electrostatic attraction given by Coulomb's law: _ Zedle) AN Eg? f Here € is the permittivity of free space. The other one is the centrifugal force, f, acting outwards. The value of this force is 2 mv gat where m is the mass of the electron and (v’/) is its radial acceleration. The condition for orbit stability is Sah Thus we ee r “anegr en4 Solid State Physics i. CONCLUSION OF RUTHERFORD’S THEORY f ‘The atom consists of a positively charged heavy nucleus surrounded by revolving negatively charged extremely light particles called electrons, like the planets round the sun, at such a speed that the mechanical centrifugal force would just balance the net excess of electrostatic attrac- tion and in consequence stability of the atom could be secured. Fig. 2.1. Circular orbit of an electron in an atom. Ill, DRAWBACKS OF THE RUTHERFORD MODEL OF THE ATOM A logical place for an electrical engineer or a physicist to begin his study of solid state physics is with the rudiments of quantum mechanics. Quantum mechanics was developed because classical mechanics failed to explain the behaviour of atoms. As an example, consider the hydrogen atom consisting of one electron and ‘one proton with an attractive Coulomb potential between them, Newton's laws of motion would allow the electron any value of energy in its orbit about the proton as long as the Coulomb attractive force which varies inversely as the square of the distance between the proton and electron is balanced by the outward centrifugal force of the electron. However, experiments on the hydrogen atom inform us that the electron appears to have only very specific or discrete values of energy. A further problem arises in regard to some other classical equations of physics (Maxwell's equations) which have to do with moving charges and electromagnetic fields. These equations predict that the negatively charged electron whirling around the proton would continuously radiate energy (in the form of light) and gradually be drawn into the proton as it slowed down. This is contrary to the fact that hydrogen atoms can exist in nature without continuously emitting light, After much trial and error, quantum mechanics was developed in 1926 and explained these discrepancies. Thus the laws of physics that are valid in the macroscopic world do not hold good in the case of microscopic particles such as electrons. Rutherford model also failed to explain the emission of radiations as light, x-rays, etc. from the atoms of different substances under certain conditions, IV. BOHR MODEL OF ATOM Hydrogen, the simplest of all elements, was investigated most extensively both experimentally and theoreti- cally. As long ago as 1885, Balmer succeeded in obtaining a simple relationship among the wave numbers of the lines in the visible region of the hydrogen spectrum. The first quantitatively correct derivation of the Balmer formula on the basis of an atomic model was given by Bohr (1913), in his theory of the hydrogen atom. This theory has played such an important role in the development of atomic physics that, even though it has been modified and extended by the later developments in quantum mechanics, it will be worthwhile to present the original simplified theory. In 1913, Niels Bohr proposed a model for the hydrogen atom which retained the earlier nuclear model of Rutherford but made further stipulations as to the behaviour of the electron. A dramatic explanation of the Rydberg spectral expression resulted. Many modern ideas about atomic and molecular structure stem from this model. Bohr suggested the following postulates to explain the electron motion in an atom and the observed spectral lines:Review of Atomic Structure 3 {) —_Anelectron in an atom moves in a circular orbit about the nucleus under the influence of Coulomb force of attraction between the electron and nucleus. The Coulombian force of attraction is bal- anced by Newtonian centrifugal force. Thus we have (Ze)fe) _ mv? anegr or (i) Anelectron cannot revolve round the nucleus in all possible orbits as suggested by the classical theory. It can revolve only in a few widely separated permitted orbits. While moving along these orbits round the nucleus, an clectron does not radiate energy. These non-radiating orbits are called stationary orbits. (ii) The permissible orbits of an electron revolving round a nucleus are those for which the angular momentum of the electron is an integral multiple of f/2n, where / is Pianck’s constant. Thus for any permitted orbit, ton(2) A A or (mn (4) m0, -o( 4) @2 ‘where m and v, are the mass and velocity of the electron, 7, the radius of the orbit and n is a positive integer, called the quantum number. The above equation is called Bohr's quantum condition. (iv) An atom radiates energy only when an electron jumps from a stationary orbit of higher energy to another of lower energy, ‘Thus if the electron jumps from an initial orbit of energy Eo a final orbit of energy E,(E,> E), the frequency of the radiation emitted is given by the relationship. hu=E,~E, where is Planck’s constant. This equation is called Bohr’s frequency condition. V. BOHR’S THEORY OF HYDROGEN ATOM Let us now apply these postulates to the classical model of the atom with a nucleus of charge (Ze). From Bohr’s first postulate, we have eee 1 MRE ie 3, Ze mnt ee (24) where Z= | for hydrogen atom. From Bohr's third postulate, the angular momentum of the electron in a permitted orbit must be an integral multiple of 4. Prom equation (2.2), we have6 Solid State Physics wee -(4) @5) ay Asal 2 Substituting this value of v, in equation (2.4), we get ah_P_ Ze? (ON Fa mr,| “ine, 27) " Hence, the radii of different stationary orbits are directly proportional to square of n (called principal quantum e number). Velocity of electron in the stationary orbits can be obtained by substituting this value of r, in equation , (ei Fig. 2.2 Bohr’s model of hydrogen atom. = ” It is now clear that the velocity of the electron is inversely proportional to the principal quantum number #. Thus electron moves at a lower speed in higher orbits and vice-versa. ‘The orbital frequency of an electron in the stationary orbits is calculated as follows: -Q se] ”Review of Atomic Structure 7 Vi. TOTAL ENERGY OF THE ELECTRON IN THE STATIONARY ORBITS ‘The electron revolving round the nucleus has both potential energy (due to its position with respect to the ‘ucleus) and kinetic energy (due to its motion). The potential energy of the electron is considered to be zero when it is at infinite distance from the nucleus. Potential energy of an electron in an orbit is given by the ‘work done in taking the electron from the distance r to infinity against the electrostatic attraction between the nucleus and the electron. This is obtained by integrating the electrostatic force of attraction between the nucleus and the electron from the limit o° to r,. ‘Thus PEE. of the electron =—f Fir)dr " 3, pee f Zee, J anegn Thatis, Ze? PE anech Similarly K.E ofthe electron = mv? ‘Substituting the value of mv? from equation (2.4), we get ze KEE ‘Thus the total energy of the electron in the n® orbit is E,=P-E+K-E ze, Ze? ie? dneor, Bneyr, BRear, ‘Substituting the value‘of r, from equation (2.7) awe] 2.10) ‘The negative sign of the energy expression shows that the electron is bound to the nucleus and some work must be done to puil it away. It further follows from equation (2.10) that as n increases, E, becomes8 Solid State Physics Jess negative and hence its algebraical value increases. The electron, therefore has minimum energy when it is in its innermost orbit, n = 1. The state of the atom with the electron revolving in the innermost orbit is called the ground or normal state and is obviously the most stable state of the atom. Vil. CALCULATION OF r, AND E, FOR HYDROGEN ATOM whe, <=" withZ=1 [Refer equation (2.7)1 n= ""RmZe* 7, = 1(6.626% 10 (8.854 x 10) "9.109 x 107") (1.602 x 10) 1, = (?)(0.529 x 10") metre @ip ‘Thus radius of the first orbit of hydrogen, r, = 0.529 10“ m. ‘This is called the Bohr radius (7). ‘Thus aa rant, ‘The energy of the electron in the n" orbit is mize = withZ=1 i aera (Refer equation (2.10) B me’ Ba whore B = ora (2.12) (9.109 x 107})(1.602 x 10°)" ‘Thus ~ pn e n? x 8(8.854 x 10)" (6.626 x 10) 2.13) when notReview of Atomic Structure 9 This corresponds to the ground state energy of the atom, and is called the ionisation potential of hydrogen atom. Similarly, the energy of the atom with the electron in the second orbit is 1.511 eV and soon. Vill. BOHR'S INTERPRETATION OF HYDROGEN SPECTRUM If an electron jumps from an outer initial orbit n, of higher energy to an inner final orbit n, of lower energy, the frequency of the radiation emitted is given by mZ'et | [met | Beg hn BER An}. hy (E-E)= mZe' nail 4] Hence hk ue ve Retain? ne mZ'e' 1 re (2.14) Tara i al sil Limes [Lod | A Bejch La ay The reciprocal of the wavelength is called the wave number. Thus v (215) Ze i ns, with Z = Lis called Rydbergconstant for hydrogen (R,,). Thus ~8E5ch (9.109 x 107") (1.602 x 10") 4 8(8.854 x 10°F (3 x 10°)(6.626x 10™) Ry = 1.0961 10" m" An atom is said to be excited, if the electron is raised to an orbit of higher energy. The electron can be completely freed from the influence of the nucleus by supplying sufficient energy and the minimum energy needed for this is called éonisation enerey. For hydrogen10. Solid State Physics Thus (2.16) ‘As long as the electron remains in its orbit, no energy is radiated, but whenever an electron jumps from an outer orbit to an inner orbit, energy is emitted in the form of radiation. When the hydrogen atom is subjected to an external source of energy, the electron jumps from lower energy state to higher energy state. The atom is said to be excited. The excited state is not stable and hence the electron returns to its ground state in about 10 second. The excess of energy is now emitted in the form of radiations of different wavelengths. In a hydrogen discharge tube there are very large number of hydrogen atoms which are excited, and radiate energy. In some atoms the electrons may jump from the second orbit to the first orbit, in some others from the third to the second or first and so on. The different wavelengths due to different transitions of the electrons constitute spectral series which are characteristics of the atom emitting them. IX. SPECTRAL SERIES OF HYDROGEN Lyman serie: ‘When electrons jump from second, third, ... etc. orbits to the first orbit, the spectral lines are in the ultra violet region. Here, n, = 1 and 1; =2, 3, ‘Thus This is identified as Lyman series, Balmer Series When electrons jump from outer orbits to the second orbit (m, = 2, n: =3, 4,5. we get lines of Balmer series = ii This series is called Balmer series and ies in the visible region of the spectrum. The first line in the series (1, = 3) is called H, line, the second line (n; = 4) is called Hp and so on.Review of Atomic Structure 11 Fig. 2.3 Quantum jumps giving rise to different spectral series of hydrogen. Paschen series in the infrared region are due to the transition of electrons from outer orbits to the third 1 4 with my = 4,5, .00 rm sen Brackett series Ifn,=4 andn, = 5,6, a WE get Brackett series lines. _ ba VER, Pon with a, = 5,6,7,8,....0te. Pfund series Ifn, =5 and n, = 6, 7, 8....we get the Pfund series lines. For this series, 1 = 1 o-r,|3 4] with n, = 67,8, ....0tc.12 Solid State Physics mye Brackett and Pfund series lie in the far infrared region of the hydrogen spectrum. By putting + 1) in each one of the series, we get the longest wavelength of the series. Similarly by putting ‘n; = in each one of the series, we get the shortest waveiength of the series (or series limit). obnee y (eV) N20 (E+ 13-6 ! } 6 (13-2) 5 3-4) 4 (12-8) 3 2-1) 2 Wo-2) 1 (0) Fig. 2.4 Energy level diagram of hydrogen. X. SHORTCOMINGS OF BOHR’S THEORY Bohr’s theory, based on circular electron orbits, was able to explain successfully a number of experimentally observed facts and has correctly predicted the spectral lines of neutral hydrogen atom and singly ionized helium atom in terms of the principal quantum number n. However, the theory fails to explain the following facts: @ Gi) Gil) tiv) W) It could not account the spectra of atoms more complex than hydrogen. It fails to give any information regarding the distribution and arrangement of electrons in atoms, I does not explain the experimentally observed variations in intensity of the spectral lines of an element. It fails to explain the transitions of electrons from one level to another, the rate at which they occur of the selection rules which apply to them. It fails to account the fine structure of spectral lines. Actually, it was found that when spectral lines emitted by an atom are examined, each line is composed of several lines closely packed together. Bohr's theory does not throw any light on itReview of Atomic Structure 13 (vi) The theory cannot be used for the quantitative study of chemical bonding. (vil) It was found that when electric or magnetic field is applied to the atom, each spectral line splits into several lines. The former one is called Stark effect while the later Zeeman effect. Bohr’s theory fails to explain these effects. Xl. SOMMERFELD’S RELATIVISTIC ATOM MODEL ‘According to Bohr, the lines of hydrogen-like spectrum should cach have a well-defined wavelength. Care- ful spectroscopic examination showed that the H. Hy and H, lines in the hydrogen spectrum are not single. Each spectra! line actually consisted of several very close lines packed together. Michelson found that under high resolution, H, line can be resolved into two close components, with a wavelength separation 0.013 nm. This is called the fine structure of the spectral lines. Bohr’s theory could not explain this fine structure. Sommérfeld succeeded partially in explaining the observed fine structure of spectral lines by intro- ducing the following main modifications in Bohr’s theory: (i) Sommerfeld suggested that the path of an electron around the nucleus, in general, is an ellipse with the nucleus at one of the foci. The circular orbits of Bohr are a special case of this. (ii) “The velocity of the electron moving in an elliptical orbit varies considerably at different parts of the orbit. This causes relativistic variation in the mass of the moving electron. Therefore Sommerfeld took into account the relativistic variation of the mass of the electron with velocity. Hence this model of the atom is called the relativistic atom model. : Xi, ELLIPTICAL ORBITS FOR HYDROGEN An electron moving in the field of the nucleus describes elliptical orbits, with the nucleus at one focus. Cir- cular orbits are only special cases of ellipses. When the electron moves along a circular orbit, the angular coordinate is sufficient to describe its motion. In an elliptical orbit, the position of the electron at any time instant is fixed by two coordinates namely the angular coordinate (9) and the radial coordinate (r). Here ris the radius vector and @ is the angle which the radius vector makes with the major axis of the ellipse. Consider an electron of mass m and linear tangential velocity v revolving in the elliptical orbit. ‘This tangential velocity of the electron can be resolved into two components: one along the radius vector called radial velocity and the other perpendicular to the radius vector called the transverse veloc- ity. Corresponding to these velocities, the electron has two ‘momenta: one along the radius vector called radial momentum and the other perpendicular to the radius vector known as azi- muthal momentum or angular momentum. So in the case of elliptic motion, both the angle @ and the radius vector r vary periodically, as shown in Fig 2.5. Fig. 2.5 Sommerfetd's mode! ofthe atom. Thus the momenta associated with both these coordinates (@ and s) may be quantized in accordance with Bohr's quantum condition. The two quantisation conditions are fosio=nd 17) fear =nh 2.18)14 Solid State Physics where n, and n, are the two quantum numbers introduced by Sommerfeld. Since they stand for one periodic system, n, +n, =n. Here n, is known as radial quantum number and n, as angular or azimuthal quantum number. n is known as principal quantum number. We have now to quantize the momenta associated with both the radial and angular coordinates. The two equations are f PAd=ah and fraranh ‘The integrals are taken over one complete cycle of variation of the respective coordinates. Both n, and n, are integers. Furthermore, the sum of m, and n, is equal to the principal quantum number n. ‘The force on the electron is due to the electrostatic attraction to the nucleus and acts along the radius vector. There is no force at right angles to this radius vector, so the transverse component of the acceleration is zero throughout the atom, Hence Thetor ($8) and ome [ 4] must be a constant. Equation (2.17) can be easily evaluated. Thus, a-n(4] (2.19) ‘This equation shows that the angular momentum of the electron is an integral multiple of + It is considerably difficult to evaluate the integral in equation (2.18). However, here. The polar equation to the ellipse is attempt is made 1_L+ecose 7 @a-e) omy where a is the semimajor axis and ¢ the eccentricity. Thus differentiating this equation with respect to 6, we : ()a) a; Ifdr) _ resing (4) a(i-e) ean ‘Substituting the value of r from equation (2,20), we getReview of Momic Structure 15 (e)-f a(t-e) je, r\do) “LO +ecose)la(l-e) 1fdr) ___esing mm (3) =e 22) Referring to equation (2.18) frdr=nh fde)onu fo( 3) Z)aqen-ne f =n 9H Aa)a)o- ‘Substituting for mr’ genre and from equation (2.22), we get rdo fol 1 aes Jaans Referring to equation (2.19) nfl 1 seat Tap ah me ¢{_esing af [ fata ae 223) put u = esing and v = The above equation may now be written as Ffude -(2)@r- ff "aul «(SES ~(S) ta. (3) f Tred (2.24) Solution of the integral:16 Solid State Physics i. aq ln L+Ecos@ Hint: Property of definite integral " ; J neytc =2 [porn it eax) = ft0) , . =O if (Qa -x) =f) Catt lo L+Ecos® f@)= In the integral Tree 1 ad faa-W~ reer O iFecoe 2 ‘thus [2° __ may be written as, , (1+ 8c089} ne aot ‘The solution of this integral is obtained as follows: ° La reuny When = 0,1 =Oand when =1,1 = 00 and ‘Substituting these values, the integral becomes "= do 2 [pr atizg whieh becomes (A) ea ary [releReview of Atomic Structure \7 =f lo (+e) +r =e) «4 ("_# ee Ooh FEE THO) pf 8 Thus equation (2.24) becomes (2.25) Thus, Q2n Equations (2.25) and (2.27) are the conditions that determine the allowed elliptical orbits. The allowed elliptical orbits are those for which the ratio of major to minor axes is that of two integers. When n, = 7, b= a and € = 0, the orbit becomes circular. n, cannot be zero, since the ellipse would then degenerate into a straight line passing through the nucleus. Also n, cannot be greater than a, since b is always less than a. Hence for a given value of m,n, can assume only n different values, which means that there can be only elliptical orbits of different eccentricities.18 Solid State Physics Xill, TOTAL ENERGY OF AN ELECTRON IN AN ELLIPTICAL ORBIT ‘The tangential velocity of the electron at any instant can be resolved into two components: one along the radius vector called the radial velocity [¢] and the other at right angle to the radius vector called the trans ~ were] ‘Thus, the radial momentum, mt, 2.28) the orbital angular momentum, P= mri (2.29) The kinetic energy of the revolving electron is given by (2.30) Again ‘Thus from equation (2.29) "|Review of Atomic Structure 19 Thus ine total energy of the electron Pe (1dr Ze c=. He amr Fdo, — on Pe [(1dr vijees Ze 2mr'l\ rd, a nes r [“]- 2mr"E, | mete? dQ. a ‘Gmer From equation (2.21) Al as] ‘lel endentt) ere Er'sin'g _ EF —cos'9) 4) “taa-ey (al-ey The term (¢—€° cos’ 9) of this equation can be further simplified by referring to equation (2.20) (1+ e¢089) = a(l-e) 7 atl-e) | 7 cos = vo [et] ‘Substituting this in equation (2.324) we get Al ltall ¢) Tle-{ a =] ldr re P ar 1 le fta m] rde) “aiu-eF | de} alle) Gl) (2.32) (2.32a) (2.33) (2.34)20 Solid State Physics Equating the coefficients of 7 and r in equations (2.34) and (2.32), we get 2mE, (2.35) % mZe* and (2.36) ‘Thus equation (2.35) becomes 237) ‘Substituting the value of (1—¢°) from equation (2.36) in equation (2.37), we get o ph [ amZe? *-2ma?| 4n &o Pe. 5.2"Ee (2.38) Again substituting for a from equation (2.36), we get Ze? ){_mZe* \f1- Bea) neo 2 [ mZe* | e) 32m es) pe ‘Substituting for (1 - €*) and pj from equations (2.25) and (2.19) respectively, we get [aeale}() E, (2.39) which is identical with the expression for the energy of the electron in a circular orbit of quantum number a. ‘Thus the introduction of elliptical orbits does not resuit in the production of new energy terms; hence no new spectral lines are to be expected because of this multiplicity of orbits. Thus the introduction of elliptical orbits gives no new energy levels and hence no new transition. Hence Sommerfeld’s attempt to explain the fine structure of spectral lines failed. But soon, on the basis of variation of mass of the electron with velocity, Sommerfeld was able to find a solution to the problem of fine structure of spectral lines. Here it is worthwhile to mention that experimental results and quantum mechanical predictions confirm that n, also assumes a value of zero, So corresponding to n, n, assumes 0, 1, 2....(n—1) values; ie., a total of n possibili- ties. In wave mechanics azimuthal quantum number n, is denoted by J. ‘The magnitude of the semi-major axis @ is obtained as follows: Equation (2.38) is ze? Bn, E,Review of Atomic Structure 21 Substituting for E, from equation (2.39) Ze? |[ Begin? wh? ey [2] = eeene =| 2.40) ‘ (z] mz | Tmzee a oh? where 5, = 0.0529 nm is the Bohr radius. Referring to the theory of ellipse, we write ao a-e) “3 baavi-e b -{*) [Refer equation(2.27) " (Al) Equations (2.40) and (2.41) show that the length of the semi-major axis is determined solely by the principal quantum number n, while the length of the semi-minor axis depends upon the azimuthal quantum number 7, as well as n, For a given value of n, the possible values of n, are 0, 1, 2...n, while. the corresponding values of 1, aren, (n=1),..0. When m, = 0, the ellipse reduces to a straight line and the electron then passes through the nucleus traversing the orbit. This leads to the collapse of the atom. The value of n, = Q is, therefore forbidden and for a given value n, n, is permitted to take only m values, 1, 2, 3,.., with 1, taking the comesponding values (n=1), (n = 2)...0. For the first orbit, n= 1: since (n, +.) = 1 and n, #0,n, = 1. Thus with n=, and n, = 0, the first orbit is a cirele as seen from equation (2.27). All the n-orbits resulting from the n possible values of n, will have the same energy £, given by equation (2.39). With n = 2, n, may have the values 1 and 2, so that there are two possible orbits for m= 2. One isn = 2, and n,= 1 — an ellipse and the other is n = 2 and n, = 2 - acircle; all these orbits have the same energy E, given by equation (2.39). Similarly with n= 3, n, will have values 1, 2 and 3, and the three possible orbits are ~ two ellipses with (n = 3, nj = 1 and m= 3, a, = 2) and one circle with n= 3, n, = 3; all these orbits have the same energy Ey. Usually the allowed orbits are described by giving values of n and n,, The three orbits for n= 3. are represented by symbols 3,, 3, and 3,, the subscript being the azimuthal quantum number (n,). In another notation used, the value of azimuthal quantum number 1, is described by the letters s, p, d. fete. The values of n, corresponding to these letters are 1, 2, 3, 4 etc, respectively. In this notation, the orbit determined by n = 3 and n, = 1 is represented by 35, Similarly 4d will represent the orbit n= 4 and n, = 3. These orbits are represented in Fig. 2.6. ‘The transitions between the orbits n = 3 and a = 2 giving H, line can now take place in six different ways. However, all these transitions have the same energy £, - E, and hence give rise to a single frequency for the H, line, according to the frequency condition. No new lines, which would explain the fine structure are therefore predicted.22. Solid State Physics Fig. 2.6 Elliptical Bohr-Sommerfeld orbits for hydrogen XIV. SOMMERFELD’S RELATIVISTIC CORRECTION ‘The velocity of an electron moving in an elliptical orbit varies from point to point in the orbit, being a max- imum when the electron is nearest to the nucleus and a minimum when it is farther away from the amucleus Furthermore, this velocity is quite wane 55 According to the theory of relativity, the variation of velocity means variation of mass of the electron. Sommerfeld, including the relativistic correction in the treatment of elliptical orbits, showed that ‘equation of the path of the electron was not simply that for an ellipse but was of the form 1 L+ec0s vo r a(i-e) where y is given by ze_f v2] This is the equation of an ellipse which precesses, ie., the major axis turns slowly about the focus (the nucleus) in the plane of the ellipse. The path of the electron is, there- fore, a rosette. It can be shown that the total energy with a princi- pal quantum number n in the relativistic theory is mZte* mz na 3ji s Ey etn atin 3] (2.42) we Begh Ly Abn Ms oS where a ks. cis a dimensionless quantity and Tegch 137 Fig. 2.7 Rosette path of the electron about the is called the fine structure constant. nucleus.Review of Atomic Structure 23 ‘The first term on the right hand side is the energy of the electron in the orbit with the principal quan- tum number n according to Bohr's theory and the second term is Sommerfeld’s relativity correction arising from the rosette motion of the electron orbit with principal quantum number m and azimuthal quantum number n,. The dependence of the total energy of the electron in its orbit as given by the equation (2.42) results in a splitting of energy levels in the atom. For a given value of 1, there will be 2 components corre- sponding to the n permitted values of n,. Hence multiplicity of spectral lines should appear in hydrogen atom. XV. FINE STRUCTURE OF H, LINE He line is due to the transition from n = 3 state to n = 2 state of hydrogen atom. For n = 3, there are three possible energy levels corresponding to the three values of 1, = 1,2 and 3. Similarly, there are two possible levels for m = 2. Therefore, theoretically six transitions are possible: 3,923,253, D5 HY}, II, and these transitions are shown in Fig. 2.8. Actually, the H, line has only three components. To make experiment and theory agree, some of the transitions have to be ruled out by some selection rule. The selee- tion rule is that n, can change only by +1 or =I. i.e., Any =21. | a ) 1 ! Fig, 2.8 Transitions and forbidden lines, XVI. DRAWBACKS OF BOHR-SOMMERFELD ATOM MODEL (®) Borhr's theory failed to explain the fine structure of spectral lines even in the simplest hydrogen atom. (i) In the case of complex atoms, Bohr-Sommerfeld theory failed to calculate the energy of the system and frequencies of radiation emitted. (ii) Sommerfeld’s modification, though gave a theoretical background of the splitting of indi- vidual spectral lines of hydrogen, still it could not predict the correct number of observed fine structure lines. (iv) Both the modets could not explain the distribution and arrangement of electrons in atoms. (¥) Both the models do not throw any light on the intensities of the spectral lines.24 Solid State Physics . (vi) Both the models could not explain anomalous Zeeman effect and Stark effect. In order to provide a satisfactory explanation of the above, the vector model of the atom was formu- lated, this being based partly on experiments, partly on an analogy and partly on empirical methods. XVI. VECTOR ATOM MODEL For explaining the complex spectra of atom and their relation to atomic structure, the vector atom model was introduced. The two distinct features of the vector atom model are: (i) the conception of spatial quantica- tion, and (ji) the spinning electron hypothesis. (i) Spatial quantization or quantization of direction According to Bohr’s theory, the orbits are quantised as regards their magnitude (i.e., their size and shape) only. Finding this theory yet inadequate to explain further experimental observations viz., the Zeeman and Stark effects in which the spectral lines could be split up under the influence of magnetic and electric fields, the idea of orientation of the orbit in space naming it ‘the space quantization’ was introduced; i.e., the direction or orientation of the orbits in space also should be quantized. To specify the orientation of the electron orbit in space, we need a fixed reference axis. This reference line is chosen as the direction of an external magnetic field that is applied to the atom. The different permitted orientations of an electron orbit are determined by the fact that the projections of the quantized orbits on the field direction must themselves be quantized, The idea of space quantization leads to an explanation of Zeeman effect. The Stern-Gerlach experiment provided an excellent proof of the space quantization of atom. The quantum number associated with the space quantization is called ‘magnetic orbital quantum numnber’ and is represented by m,. (ii) Spinning electron To account for further hyperfine details in the atomic spectra of multi-cleetron atoms, Uhlenbeck and Goudsmit (1925) showed that the remaining difficulties could be resolved by assuming that the electrons were spinning about their own axes like a top, while traversing their orbits thus resulting in slight changes of energy. The spin of the electron is analogous to the spinning of a planet about its own axis as it moves in an elliptical orbit around the sun. In other words, the electron is endowed with a spin motion over and above the orbital motion. According to the quantum theory, the spin motion like the orbital motion, is to be quan- tized which will therefore introduce a new quantum number called the magnetic spin quantum number, denoted by m, XVII THE CHARACTERISTIC QUANTUM NUMBERS ‘The state of the electron around the nucleus in terms of its location relative to the nucleus and the energy associated with it is described by a set of quantum numbers. Each electron is characterised by four impor- tant quantum numbers called the total or principal quantum number, the orbital or azimushal quantum number, the magnetic orbital quantum number and the magnetic spin quantum number. The significance of these quantum numbers in terms of size, shape, orientation of orbitals in space and spin around the nucleus is now described briefly. (i) The total or principal quantum number (n) This is identical with the one used in Boht-Sommerfeld’s theory. It can take values 1, 2, 3, 4...0. This specifies the major axis of the ellipse with which the energy of the electron is associated and hence pertains to the main energy level or shell. These energy levels having values of n= 1, 2, 3, 4, etc. as we go away from the nucteus are denoted by symbols K, L. M, N, etc. The energy (E) is inversely proportional to n?. That is,Review of Atomic Structure 25 (ii) The orbital quantum number (i) This quantum number is an integer and for a given value of n, it can take any of the n values 0,1, 2, 3, (n-1). By comparing these values with the values of the azimuthal quantum number n, of Sommerfeld’s theory, itis seen that / is nothing but (n,~ 1). J specifies the minor axis of the ellipse and is equal to (n ~ 1) when the orbit is circular. It also divides the main shell into n slightly different energy levels or sub-shells so that the number of sub-shells in a main shell is given by its principal quantum number. Thus the shell with principal quantum number n = 1 or K-shel! has only one sub-shell designated as s-sub-shell and in that case 1 0. This quantum number specifies the mechanical angular momentum of the electron and hence it is also called the angular momentum quantum number. The orbital angular momentum p; associated with different orbits are ath, where / =0,1,2,... ete According to quantum mechanical results, the value of orbital angular momentum p; is not equal to but given by im pe warn £) 2, The second principal shell or the L-shell will have two sub-shells having values of ! = 0 and f = 1. ‘They are designated as s- and p-sub-shells. Similarly, the M principal shell has three sub shells with values of = 0, 1, and 2, and they are named as s- p- and d- sub shells respectively. Thus the n-sub shells of the n™ principal shell have the / values of 0, 1, 2...(n=1). It may further be noted shat s-sub-shell is lower in energy than p-sub shell and the latter is lower in energy than the d-sub shell and so on. (ili) Magnetic orbital quantum number (m) This quantum number specifies the orientation of the electron in an external magnetic field; ie., this quantum ° number specifies the space orientation of the electron’s 2 plane elliptical orbit but has no effect on energy levels. It Pi originated in the evidences of slight differences between almost identical energy levels obtained from the Zeeman 1 effect; i.e., the splitting of spectral lines when a light bs | source is placed in a strong magnetic field and from the ° corresponding Stark effect produced by the application of SX fn intense clectric field. In these cases, the electrons 4 because of their magnetic moments will experience torques tending to orient them so that the spin and the = angular momentum vectors will take up definite positions x in space with respect to the magnetic field thus introduc- ing fresh levels, These extra sub shells are denoted by the Fig. 2.9 Projection of orbital quantum vector in magnetic orbital quantum number m,. For a given value of the direction of the magnetic field. the orbital quantum number /, m, can take any of the26 Solid State Physics (21+ 1) values 2, (1), (f= 2)..0,0,—1,—2, n=l. This means that m, can assume (21+ 1) values or the vector I can have (21+ 1) orientations. For example if ! = 1, the permitted orientations of f are 3 for which m, has the values +1, 0, -1. This is illustrated in Fig. 2.9, for != 3. The angle @ between | and B is given by I cos @ = my. ‘The permitted orientations of the / vector relative to the field direction B is (21 + 1). For example, if I= 3, the permitted orientations of f are 7, for which m, = 3, 2, 1, 0,1, -2,-3. Hence the £ vector can take only the seven directions shown in Fig. 2.9. { cannot be inclined to B at any other angle, This is called spatial quantization. (iv) The magnetic spin quantum number (m,) This quantum number specifies the orientation of the electron spin axis relative to the same frame of refer- ence as used for m,. The angular momentum can assume only two possible positions with respect to the magnetic field, clockwise or anticlockwise, that is, it may be parallel or antiparallel to it, viz, oppositely directed to it. Its projection along the direction of the magnetic field is denoted by m, which is called the magnetic spin quantum number and can have only the values + or 4 as illustrated in Fig. 2.10, s0 that the difference in the spin quantum numbers for two electrons in any orbit is unity. The spin angular momentum of the electron is given by h 1 P.=5 5 where $= 5 ‘According to wave mechanics, the spin angular momentum p, of the electron is given by o.=\ieri( £) ‘Thus the four quantum numbers specified above define completely the state of any electron in a given atom. . XIX. THE PAULI’S EXCLUSION PRINCIPLE The generalised principle that governs the electronic configuration of atoms having more than one electron hhas been summarised in the exclusion principle, which was suggested by Wolfgang Pauli in 1925. According to this principle, no two electrons in an tso- B lated atom can exist in the same quantum state, This principle is empirical and cannot be directly verified. But its universal acceptance rests on the fact that all the meee deductions which have been made from it have been either subjected to experimental verification of fit into a logical account of the theoretical physics of the struc ture’of the atom. Pauli's principle implies that no two electrons in the same atom can have the same values of Msa-} the four quantum numbers n, l, ny, m,. At least one quantum number must be different. To illustrate this principle, let us take the case of helium atom which has two electrons. These electrons occupy n = 1 ofbit or K-shell. Clearly for n = 1,1 =0 and therefore, m,=0. Fig. 2.10 Projection of the spin vector s in the direc- tion of the magnetic field showing the two possible values of m,Review of Atomic Structure 27 1 But m, can have two values, namely, +} and -2. Hence, one electron has = 1,1 =0,m, =0,m, = +5 and the other electrons has a = I, =O.m,=-4. ‘Quantum representation of the electrons in the K-shell is illus- wwated in Fig. 2.11. Quantum state Electron Pictorial representation Configuration @ a=, Om = 1st oO (b) n=1,f=0,m,=0,m, 5 as Qa 1 (©) m=1,1=0,m,=0,m,=25 we ® Fig. 2.11 Quantum representation of electrons in K-shell. XX. APPLICATION OF PAULI’S EXCLUSION PRINCIPLE (@ Find the maximum number ot electrons that 1 = 2 orbit can accomodate according to Pauli’s exclusion principle. For L- shell n=2 no 2 2 2 2 2 2 2 2 ' oO 1 to dot ta m 0 O-1 -l 1 t 0 0 ~ Ee tei bs * 2 2 2 2 2 2 2 2 It can now be seen that in no two vertical columns, all the four values of quantum numbers are sdentical, ‘This means that the maximum number of electrons that can exist in L-shell is 8. (ii) Maximum number of electrons in orbitals or sub shells Consider an orbit with principal quantum number n and orbital quantum number !. For finding the number of electrons in any orbital, it is clear that the values of nm and J are fixed. Only the values of nm and m, can change. Now 110+! including zero,28 Solid State Physics Thus for a given value of f, there are (2! + 1) values of m, Now for each value of m, m, can have only two values, namely; +4,—2 22 Hence, there can be only 2(2! + 1) different combinations of (n, /, my m,)- Thus the maximum number of electrons in any sub-shell with orbital quantum number / = 2(2/ + 1). For example: sub shell (/ = 0) can have a maximum of 2(2! + 1) =2 electrons. p-sub shell (J = 1) can have a maximum of 2(28 + 1) = 6 electrons and so on. (til) Maximum number of electrons in main shells The main shell consists of a number of sub-shells, called orbitals. According to Pauli's exclusion principle the maximum number of clectrons in an orbit with principal quantum number n is equal to 2n*, This can be provedias under: Consider an orbit with principal quantum number n and orbital quantum number J. It has already been shown that the maximum number of electrons in an orbital is equal to 2(2! + 1) with 1 = 0, 1, 2,.. (1-1). ‘Thus the total number of electrons with principal quantum number n is given by dagt Ey 22+) imo =2'F'aen wales. Fs) |e) ] 2fp'fi's"$3] [ 2, fe (2422) =2n? ‘Table 2. — The distribution of electrons in the various states a 1 m 1 Number of electrons in Number of 01,2 (-t10 +1) mt5 sub-shells electrons in w(t) main shells (2nt), 1 0 0 +12 2 ie UK) 1 o 0 -2 2 o oO +12 2 ae 2 0 o In 2 I -1 +12 2 1 -1 We BL) 2 I o +12 2 1 0 -12 6 apt 2 t 1 +12 2 I 1 -12 3 0 0 +2 2 3 3 0 o 124@ ‘You have either reached 3 page that is unavailable for viewing or reached your viewing limit for this book.4@ ‘You have either reached 3 page that is unavailable for viewing or reached your viewing limit for this book.4@ ‘You have either reached 3 page that is unavailable for viewing or reached your viewing limit for this book.32. Solid State Physics RIRARASAIIS FT SSRAR agiag SSsse > abs |. B2o0/8 mole ls (Contd..) [Flere cron cucececslesereccrerfercecieret occ cia wlfjonofeleeeeeisesesisesesisesss alajoovcclovocvlovevvloovvvlocove Table 2. B off SZES8/S8S2R5|28a>8 ‘Name of Symbol Atomic Distribution of Electrons within the shells 1" 6 2 a 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 Element 2 Palladium Sitver Indium io (Cadmium 2 anluldull FRRARARRASSSSSSSSSSR Alomie Number 1 26 2 28 29 04@ ‘You have either reached 3 page that is unavailable for viewing or reached your viewing limit for this book.34. Solid State Physics wfSPr cree ee rape pt feameonfe oe Qed =[Sleoaeeleeees|eeees(eeeeeieeeos © 2 alSjooccvlovcev[ovscelcoooe|ovove Table 2.8 (Conid.) Distribution of Elecirons within the shells s 8 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 weight ‘Symbol Atomic o[xe22|neaze|aae ee é e| 828 eias § lalla ‘Name of Element 2 Osmium {ridium Platinum Gold Mercury ‘Thallium Lead Bismuth Polonium Atomic Number 1 16 n 8 p 80 81 82 3 4 85 86 37 88 39 90, a1 n 3 4 95 96 \] 97 8 9Review of Atomic Structure 35 ‘adowost puno} Aquouu0s sou ax 40} pareTnoqeD St S9seD asaqp tH suOHMoN Jo AIquIMU ALL“ -suoneas seajonu wr Aqperoutum pasedoad usoq 2Aey yng ‘aMreU ut mn290 jou Op sIsoypUaREC wi! LOAKT axe sIyiOM ORUOIE asOYM SIUDWI]D IY, “TZ “ajqeisun ame, poyrew swuawery “1 THON 9 tno 9 co 9 to te eH WME SOT 9 tm Oo 9 co 9 to te BX umMAcIERIMY — 401 9 cm oO 9 fo 9 f 9 FCs) mT URE] — FOF 9 2m oO 9 FO 9 FT 9 TZ CE) — ON MHEGON —ZOT 9 tw of 9 cf Oo 9 t 9 ZF 2 se) AW UMA 101 % un ot aw oO 6 8 F 8 S + € 2 1 7 po # 3 p @ 8s yp @ 6 p dos as o 4 ° N « 1 4 swoumau mBion nuauryq —soquny fe saqueny S12ys 2p way sucursary fo uounquiig —mnwory — joquds — fo muny —-Inaary pmo) aces36 Solid State Physics sD GSO Usd sd Gse (5D Ur (xd (ere) (re) CED) CORE CED) seOTET (Lew) “TN PAO SNS for Olli Hi‘ SO Vee UGHLL WELT FESR STI OLSFOI OSZOI HORST STLSI GIST SCOSE CH) HHI LOSI crOFI 16'REt 7 & M BF Oh ff @ PO Mm WS Wd PN OFT soy “mo 6 9 © © 8 8 8 3 9 © & 8 8 We ow ex) - Yo” forse 8k (22 (OID) MOI) BROT GLO LEO G5'0OT 196961 SOS6I TLL TOL TORI SFE SPORT GHRLT seLEI so6zET my fd a uw HH wo Ww 1 9 WM mM fl TH + ta 9 8s ss ow & ff 1 oO eo &@ U& M&M HH HW H& Wiis 8% ss 98 OCTET FO6SI OFLTI SLIZI GFBIL SPIT OFTII OLTLOT F901 SOBZOI LOTOL (65) POSE ISTE WIG SOK TILA LSB x 1 % 3 % 4 PR BY PLO We MH OL ON WN OK OS 6 6 ww iS 0 G6 & tt OF Sr Ww & w@w It OO & M Lf § ES GOEL BRL WHHTL STL WED (ESD HED LHS ECORS LYTSS BEETS B66'TS THEOS O6'LF 956FF ROOF ZOI'6E ao 8 8 D DW FZ M9 N DO WA W D A HW BW DH YF * se om fc cw lt Oo & & & MW © ww &@ WwW w we HF F BHEGE ESYSE FOOTE BCLEOE 9608T S18697 SUEY 686te Ww ON ame zis 669 aon ’ eo ot 4640071 4 ot 0 1 dos) pourd MUL POUL =O TOIL4@ ‘You have either reached 3 page that is unavailable for viewing or reached your viewing limit for this book.38 Solid State Physics shell begins to form and a new row of periodic table commences. The elements in this row add their elec- trons to the second shell untit it is completely filled at neon. The order of filling may be completely under- stood by examining Tables 2B. It is also found that when a new shell begins to form in the structure of the atom, the element in question commences a new row in the periodic table. ‘An important effect occurs in the elements immediately following argon. To complete the third shell, 10 more electrons are required to occupy the 3d states. For these elements, however, 4s energy level is slightly lower than the 3d, and so fourth shell begins to form before the third shell is filled. Thus a new period commences with an alkali metal, potassium, and an alkaline earth metal, calcium. In the following series of elements, extending to copper, the 3d states become increasingly occupied. Hence, there is a large ‘group in this period with only one or two electrons in the outermost shell. All these elements are metals, and those in which the third shell is expanding from 8 to 18 electrons are known as transition metals. The same sort of behaviour is found in the subsequent rows of the periodic table. The Ss states are occupied before the 4/ and 6s states before the Sd. As a result, two additional groups of transition metals are obtained. In the final long period, the situation is completed by the fact that during filling of the Sd states in the last group of transition metals, the 4f states begin to be occupied. This results in a group of elements known as the rare earths. XXII, ~WAVE-MECHANICAL CONCEPT OF THE ATOM ‘There have been important developments since the Bohr-Sommerfeld theory. These developments have proposed treatments entirely foreign to the Bohr-Sommerfeld picture and these have led to even more satis- factory results from an analytical point of view. The modifications were started when de Broglie proposed that particles, such as electrons, possessed many properties of waves. He concluded theoretically that a particle of mass m now moving with a velocity v would behave as a wave having a wavelength b my This wave-mechanical treatment of the atom illuminates many of the odd ad hoc assumptions made in the pre- vious sections. Instead of assuming the electron to be moving in a fixed stationary orbit it was imagined to generate a series of waves as it revolved round the nucleus in any permissible orbit. In order that the waves should not cancel each other by interference in any permissible orbit, the elec- tron must move in such a manner as to produce a stand- ing wave in the orbit. This will happen only if the electron wavefront fills the circumference as in Fig. 2.13 where there are an integral number of wavelengths. Thus the circumference must contain an integral number of waves. Fig. 2.13 De Broglie's stationary wave quantized orbits, Thus 2nr = nA where r is the radius of the permitted orbit and 7 an integer. Substituting JA torn, we getReview of Atomic Structure 39 2.43) But mvr is the angular momentum of the electron regarded as a particle. Thus we see that the wave mechanical picture leads to Bohr’s postulate regarding the quantization of orbits-that the only permitted orbits are those angular momenta are equal to an integral multiple of x OBJECTIVE QUESTIONS 1. If f,and f, are the frequencies of the electron in the first and second orbits of hydrogen atom respec- tively, then (f/f) is @ 8 b) 2 © 4 @ 1 2 The total energy of the electron in the n™ orbit of hydrogen atom is 2 2 (a) = ees ® 4m Ey 1, oe 4neqr'n e e a - © & fo Ta O -m fF 3. The kinetic energy of an electron in an atom is {@) half of its potential energy (b) twice its potential energy (©) equal to its potential energy (@) thrice its potential energy 4, If the radius of the first orbit in hydrogen atom is 0.05 nm, the radius of the first orbit in helium atom is (@) 0.025 nm () 0.05 nm ©) Inm (4) none of these 5. The numerical value of the radius of the first orbit of hydrogen is @) 0529 nm () 0.0529 A (©) 529A @) 0.0529 am 6. The total energy of the electron in hydrogen atom is (a) = (3.6/n) eV (b) (13.6/n) eV fe) =(13.6/n?) eV (@) (13.6/n") eV 7 ‘The ratio of frequencies of the first line of the Lyman series and the first line of Balmer series is (a) 2715 (b) 278 © 87 (@) 427 8. When an electron jumps from the fourth orbit to the second orbit, one gets (a) the first line of pfund series4@ ‘You have either reached 3 page that is unavailable for viewing or reached your viewing limit for this book.4@ ‘You have either reached 3 page that is unavailable for viewing or reached your viewing limit for this book.42. Solid State Physics 22. 28, Seabee ps 10. u. 12. 13. 14. 15. 16. 17, 18. 19. 21 2. If, and n for an electron in an elliptical orbit are 1 and 2 respectively, then the ratio of semi-major axis and semi-minor axis is @ 2 (b) 05 © @ 2 4 electron volt is (@ 2x10" joule (b) 64x 10" joule (©) 3.2% 10°" joule (@) 64x10" joule If the principal quantum number and the azimuthal quantum number in the relativistic model of the atom are 3 and J respectively, then the magnitude of the semi-minor axis b in terms of the semi-major axis a is given by (a) b=al3 (b) b= 2a/3 (©) b=ald @) bea SHORT QUESTIONS Discuss the drawbacks of Rutherford’s classical theory of the atom. Give the important features of Bohr's model of atomic structure. Give the postulates of Bohr to explain the structure of atom. What are the various quantum numbers used to describe the electronic energy levels in an atom? What do the symbols s, p, d,f..stand for? Show that the circumference of an electron orbit in a hydrogen atom is an integral multiple of the de Broglie wavelength of the electron in orbit. Find the energy required to remove the electron from the normal hydrogen atom, How do you explain the origin of spectral lines in hydrogen? How is the fine structure of spectral lines accounted? Compute the limit of the Balmer series in hydrogen spectrum. Give the expression for Rydberg constant for hydrogen. How does this constant differ for singly ionised helium? Outline the nature of the relativistic hydrogen orbit. Explain the fine structure of H, line of the Balmer series. Calculate the time taken by the electron to traverse the first Bohr’s orbit in hydrogen spectrum. ‘What is the frequency of radiation when the electron jumps from the third orbit to the second? ‘The energy of the electron in the permitted orbits of hydrogen atom is given by the equation (bin?) with B =2.179x 10" joule. Give the significance of the negative sign. The first member of Balmer series of hydrogen has a waveleagth 656.3 om. Calculaie the wavelength of the second member. ‘What are the salient features of Bohr-sommerfeld atom model? Write down Sommerfeld’s expression for the energy of the electron applying relativistic correction. Discuss the significance of this expression with that of Bohr. Explain spatial quantization and spinning of electron. Discuss briefly vector atom model. ‘What do you understand by ionisation energy? On what factors does it depend?RAEB 2 - v 2 Review of Atomic Structure 43 Explain Pauli’s exclusion principle as applied to electrons in atoms. Give the electron configuration of the elements sodium and copper. Explain why neon is an inert gas. Discuss briefly the wave-mechanical concept of the atom. REVIEW QUESTIONS Give an account of Rutherford's model of the atom. What are the major deficiencies in Rutherford's nuclear mode!? How are they overcome by Bohr? Derive the mathematical expression for energy of the electron in hydrogen atom. Give the interpreta- tion of the negative sign. Discuss Bohr's theory of hydrogen atom and derive an expression for the radius of the first Bobr orbit for the normal hydrogen atom. State Bohr’s fundamental postulates to explain the structure of hydrogen atom. Obtain the general expression for the radii of the Bohr’s orbits and orbital frequencies of the electrons occupying them. Give an account of Bobr's theory of hydrogen spectra and obtain expressions for the spectral series of hydrogen. Discuss the postulates of Bohr's theory of hydrogen atom and derive an expression for the wave number of Balmer lines of hydrogen spectrum. . Outline Bohr’s theory of hydrogen atom and show how it accounts for the observed spectrum of hydrogen. Based on Bohr's assumptions obtain the expression for the orbital energy of an electron in the hydro- gen atom. Also account for the different series of spectral lines of the hydrogen atom. Obtain a general expression for the radii of the Bohr orbits and for the orbital frequencies. Explain H-spectrum on the basis of Bohr’s theory. Describe Bohr's atom model. Assuming that the nucleus is infinitely heavy and the electron has mass mm and charge e, find out the energy of the electrons moving in the n® orbit. Calculate the ionisation potential of hydrogen atom, | Describe the Bohr's theory of hydrogen atom. How is it successful in explaining the spectrum of hydrogen atom? . What is meant by a spectral series? Give the formula and show how the spectral series of hydrogen arise. Illustrate with energy level diagrams. . Give the theory of the elliptical orbits relating to the hydrogen atom. Explain the fine structure of the H, line of the Balmer series. |. Outline the nature of the relativistic hydrogen orbit. Explain the fine structure of the H, line due to relativity correction. .. Give an account of Bohr-Sommerfeld mode! of elliptical electron orbits of hydrogen atom. How does it account for the fine structure of hydrogen atom? ‘What do you mean by fine structure of spectral lines? Give an account of Bohr-Sommerfeld atom model. Explain how could it explain the observed spectral lines. . Explain spatial quantization and spinning of electrons. State and explain the significance of the four quantum numbers. How are they inter-related? 3. Discuss briefly vector atom model. State Pauli’s exclusion principle and explain how it helped in fix- ing up the electronic configuration of the elements in the periodic table.4@ ‘You have either reached 3 page that is unavailable for viewing or reached your viewing limit for this book.10. te 12, 13, 4 15. 16. . Review of Atomic Structure 45 PROBLEMS |. Calculate for the hydrogen atom (i) velocity of the electron in the ground state (ii) radius of the orbit of the electron in the ground state. (iii) time taken for the electron to traverse the first Bohr orbit. ‘At what speed must the electron revolve round the nucleus of the hydrogen in its ground state in order that it may not be pulled into the nucleus by electrostatic attraction (Given: radius of first Bohr orbit is, 0.052 nm). Electrons of energies 10.2 eV and 12.09 eV can cause radiation to be emitted from hydrogen atoms. Calculate in each case, the principal quantum number of the orbit to which an electron in the hydro- ‘gen atom is raised and the wavelength of the radiation emitted if it drops back to the ground state The critical potential of hydrogen is 13.05 eV. Calculate the wavelength of the radiations emitted by hydrogen atom bombarded by an electron of corresponding energy. Show that for large values of principal quantum number, the frequency of an electron rotating in adjacent energy levels of hydrogen atom and the radiated frequecies for a transition between these levels, all approach the same value. How many revolutions does an electron in the n =2 state of a hydrogen atom make before dropping to the m = 1 state? (The average lifetime of an excited state is about 10°). A single electron revolves around a stationary nucleus of charge +Ze. It requires 47.2 eV to excite the electron from the second Bohr orbit to the third Bohr orbit. Calculate (i) the value of Z (ii) the energy required to excite the electron from third to fourth Bohr orbit (iii) the wavelength of the electromag- netic radiation required to remove the electron from the first Bohr orbit to infinity (iv) the radius of the first Bohr orbit (v) the kinetic energy, potential energy and the angular momentum of the electron in the first Bohe orbit . Calculate the frequency of radiation, and also the wave number, when the electron jumps from the third orbit to the second orbit of hydrogen atom. . The first member of the Balmer series of hydrogen has a wavelength 653.3 nm. Calculate the wave- length of its second member. Calculate the ionisation potential of hydrogen from the first principle Calculate the shortest wavelength of the Balmer series (limit of Balmer series) and the largest wave- length of Lyman series. Neglecting reduced mass correction, show that (i) the short-wavelength limit of the Lyman series. (n= 1) of hydrogen is the same as that of Balmer series (n-= 2) of ionised helium and (ji) that the wavelength of the first line of this helium series is 1.35 times the wavelength of the first line of the Lyman series, The lowest two excited states of hydrogen atom are 10.2 and 12.0 eV above the ground state; calcu- late the wavelength of radiation that could be produced by transition between these states and the ground state. Calculate the magnetic moment associated with the first orbit of Bohr in the case of hydrogen Give the electronic configurations of H, Li, C and Si. The atomic weights and densities of aluminium and copper are 26.98 and 63.54 and 2700 kg/m’ and 8960 kg/m? respectively. Calculate the number of atoms present in unit volume of aluminium and copper Calculate the magnetic moment due to orbital motion of the electron. Energy in a Bohr orbit is given by 2. where B = 2.179 10°" J, ”46. Solid State Physics Calculate the frequency of radiation and also the wave number, when the electron jumps from the orbit to the second. 19. Give a quick estimation of the binding energies of the hydrogen atom from de Broglie's hypothesis. 20. How much energy is required to raise the hydrogen atom from the ground state n = 1 to the first excited state n = 2? What is the wavelength of the line emitted if the atom returned to the ground state from the excited state?CHAPTER 3 INTERATOMIC FORCES AND BONDINGS IN SOLIDS |. INTRODUCTION Many solids are aggregates of atoms. The arrangement of atoms in any solid material is determined by the character, strength and directionality of the binding forces, cohesive forces or chemical bonds. The bonds are made of attractive and repulsive forces that tend to hold the adjacent atoms or atomic units at a particular spacing such that the opposite forces just balance; and the process of holding them together is known as bonding. Since the particular type of bonding within a materia plays a major role in determining the physi- cal, chemical and clectrical properties of material, the materials engineer must possess a sound working knowledge of the types of bonding in materials. i. FORCES BETWEEN ATOMS ‘The main problem now is to account for the origin of binding forces which bind the atoms in a molecule and also the forces which bind the molecules in a solid. Electrical forces are responsible in binding the atoms and molecules giving different solid structures, Magnetic forces have only a weak effect in cohesion, and gravi- tational forces are negligible. A crystal of NaC! is more stable than a collection of free Na and Cl atoms. Similarly, a germanium crystal is more stable than a collection of germanium atoms. This implies that germanium atoms attract each other when they get close to each other; i.c., an attractive interatomic force exists which holds the atoms together, This is the force responsible for crystal formation. This also means that the energy of the crystal is lower than that of the free atoms by an amount equal to the energy required to pull the crystal apart into a set of free atoms. This is called the binding energy (also the cohesive energy of the crystal). ‘The forces between atoms can be of two kinds: attractive forces which keep the atoms together, and repulsive forces which come into play when the solid is compressed. The potential, or stored internal energy of a material is the sum of the individual energies of the atoms plus their interaction energy. When the atoms are all in the ground state and infinitely far apart so that they do not interact with cach other to form a solid, the potential energy is zero, since this is inversely proportional to some power of the distance of separation. ‘Assuming that the atoms consist of moving electric charges, one of the following two things can happen as the atoms approach each other. Either they attract or repel each other. The potential energy due to the attraction is negative, since the atoms do the work of attraction. The repulsive energy is positive since ‘external work must be done to bring the atoms together and it is inversely proportional to some power of the48° Solid State Physics interatomic separation r. The net potential energy is the sum of both terms. ‘This may be illustrated by considering the following model: Suppose two atoms A and B exert attrac tive and repulsive forces on each other such that the bonding force F, between the atoms may be represented as AB FO= 4-5 oy With N > Mf an where r is the centre to centre spacing between the atoms and A, B, M and N are constants characteristic of the molecule. The first term represents the attractive force and the second term the repulsive force. Near the equilibrium position the second term must increase more rapidly for diminishing values of r than does the first, and N is necessarily greater than M. Since the attractive forces in interatoraic bonds are largely elec- trostatic, M is usually 2 as per Coulomb's law and the value of NV is usually 7 to 10. The equilibrium spacing, ro, of the . given system is obtained as follows: F ‘Attractive force A+ Repulsive torce Fig. 3.1 Variation of interatomic force with interatomic spacing, (2) lll. COHESION OF ATOMS AND COHESIVE ENERGY ‘The potential energy representing the interaction between the two atoms varies greatly with the interatomic spacing and is obtained by integrating equation (3.1). Thus we [row {[S-8 = far Br" drInteratomic Forces and Bondings in Solids 49 Be¥ N ede Satec 3) +0 where qe say MAM OL and nN. Setting U = 0 when r =o», we find C=0 and (3.4) Here ris the distance between the centres of the atoms; n and m are positive numbers, ais a positive constant which determines the strength of the attractive force and 6 is a positive constant which determines the strength of the repulsive force. ‘The condition under which the par- Y(r) ticles form a stable lattice is that the func- tion U(r) exhibits a minimum for a finite value of ras shown in Fig. 3.2. If this t minimum exists, then the two atoms form a stable lattice, say a molecule. ‘ b i ne =a vere Isive energy, Uz 7 utr) == +B ™ Let r be the distance between the atoms for this minimum U(r) to occur. This spacing fq is known as equilibrium spacing of the system. This minimum energy Ui, at 1 = rq is negative and hence the energy needed to dissociate the molecule then equals the positive quantity of (—U,,,)- The minimum for U(r) occurs only if m and n satisfy the condition, Fig. 3.2 Variation of potential energy with spacing a>m 5) Condition (3.5) implies that the attractive force should vary more slowly with r than the repulsive force. This is obvious from the curves for attractive and repulsive forces shown in Fig. 3.1. The above said condition may be established mathematically as follows: _Lrttractive energy, Uj=~ + d uey=—S0% U(?) exhibits a minimum for r = 7, ‘Thus4@ ‘You have either reached 3 page that is unavailable for viewing or reached your viewing limit for this book.Interatamic Forces and Bondings in Solids 51 “ (| -zh-Shre “ a-(3(3) see and) mete “PCa wn a(t}{i] In conclusion, it may thus be said that the forces of repulsion are the result of interpenetration of outer electronic shells between atoms, ions and molecules when they approach one another each in interatomic or intermolecular distances. The forces of attraction are due to interaction between outer electrons of the two atoms, resulting in the formation of a sufficiently stable aggregate which can be considered as an indepen- dent molecular species. Thus all stable arrangements of atoms in solids are such that the potential energy is a minimum. This is one way of explaining the cohesion of atoms in solid aggregates. Dissociation may occur as a result of strong electric fields and mechanical strains or at high temperature. For example, 4.4 eV of energy is required to break one (HC!) bond, or 420 x 10° ki/k mol. V. BONDING iN SOLIDS From experience one knows that solids are usually moderately strong and slightly elastic structures. Thus the individual atoms must be held together in solids by interatomic forces or bonds. However, in addition to these attractive forces there must be a repulsive force because solids are not easily compressed. The attrac tive forees between the constituent particles in solids are basically electrostatic in origin and the classifica- tion of the different types of bonding is strongly dependent on the electronic structure of the atoms concerned, and hence directly related to the periodic table. ‘A solid is composed of billions of atoms packed closely together and the characteristic properties of this state of matter can be accounted for by their proximity and the forces of attractions that hold the atoms together. The importance of these attractions is evident when we consider a piece of copper wire of which each gram contains (6.025 x 10”/63.54 atoms under normal conditions; the forces of attraction that bind these atoms are very strong. If this is not true, the atoms will easily disintegrate or crumble or the metal will deform under small loads. According to the strength and directionality, chemical bonds are grouped into primary and secondary.$2. Solid State Physics Primary bonds by virtue of their nature are interatomic bonds, whereas secondary bonds are intermolecular bonds. The attractive forces in primary bonds are directly associated with the valence electrons. The outer shell, which contains the valence electrons, is in a high energy state and hence relatively unstable. If it can acquire more electrons to bring the total upto eight, or lose all its electrons to another, it become stable. This is how atomic or primary bonds are formed. In fact, each bond is a direct consequence of the exchange or sharing of valence electrons. ‘The study of the solid structure reveals that there are three strong principal types of primary bonds: tonic, covalent and metallic. These bonds are distinguished on the basis of the positions assumed by the bond electrons during the formation of the bond. van der Waals and hydrogen bonds are typical examples of secondary bonds and they result from intermolecular attraction. The bonding energy or the cohesive energy is defined as the energy of formation of one kmol of a substance from its atoms or ions. It is equat but opposite in sign to the energy of dissociation of the substance. The bond energy can be calculated as the ‘energy of the atoms or ions at the equilibrium spacing in the crystal structure, using the state of infinite sep- aration of the atoms or ions as the zero potential. The strength of a bond is best measured by the energy required to break it, that is, the amount of heat which must be supplied to vaporize the solid (infinite separation) and hence separate the constituent atoms. The melting points and the boiling points of the ele- ments are dependent on the strength of the bond. Generally, the stronger the bond, the higher are the melting. and boiling points. Vi. IONIC BONDING Perhaps ionic or heteropolar bonding is the simplest type of chemical bonding to visualize since it is almost totally electrostatic in nature. It occurs between electropositive elements (metals; i. those elements on the left side of the periodic table) and electronegative elements (non-metals; i.e., those on the right side of the periodic table). NaCI and MgO are examples of solids in which ionic bonding dominates. ‘The criterion for ionic bonding is the difference in electronegativity (the tendency to acquire elec- trons). An ionic bond is really the attractive force existing between a positive and a negative ion when they are brought into close proximity. These ions, of course, are formed when the atoms involved lose or gain electrons in order to stabilise their outer shell electron configuration. A typical example of an ionic bond is the bond between the positive sodium ion and the negative chlorine ion in sodium chloride. The white soft metal Na has the following electron configuration: K(2)L(8)M()). This atom has a low ionisation energy and hence easily loses an electron; the other atom chlorine (K(2)L(8)M(7)}, has a high electron affinity and strongly tends to acquire an electron. Suppose @ chlorine atom and a sodium atom approach each other. This occurs when sodium burns in an atmosphere of chlorine. The sodium gives up its valence electron to the chlorine, each of the resulting ions then has a stable filled shell of outer electrons, and a strong electrostatic attraction is set up that bonds the Na* cation and the CT anion into a very stable molecule (NaCI) at the equilibrium spacing. The reaction is represented by Na+Cl— Na’ +CI > NaCl Since chlorine exists as molecules, the chemical reaction must be written as ‘2Na+Cl, -> 2Na’ + 2CT — 2NaCl To release the valence electrons, a kmol of free sodium atoms requires an expenditure of energy, 1 = 496% 10° kJ (this quantity is the first ionisation energy per kmol of Na atoms). Acquisition of the elec- trons by a kmol of free chlorine atoms results in a release of energy, E, = 349% 10°KI. Thus, to initiate a4@ ‘You have either reached 3 page that is unavailable for viewing or reached your viewing limit for this book.54 Solid State Physics 2 s (c)Ionic molecule Fig. 3.3 Schematic representation of the formation of an ionic molecule of sodium chloride, 69) (62x10) |e lea alee 7 [ (1.602 107 ev 4n(8.85 x 10 x2.4)(1.602 x 10" =-6eV ‘Thus the energy released in the formation of NaCI molecule starting from neutral Na and Cl atoms having zero potential energies is (5.1 - 3.6 - 6) = - 4.5 eV. Schematically Nat + Cit —> Na + Cl +45eV— Nac) e003 €0.24nm—> This is the energy released. Thus the entire process evolves an energy of 6 - 1.5 = 4.5 eV. This means that to dissociate a NaCI molecule into Na and Cl ions, it requires an energy of 4.5 eV. Bond lengths and bond energies of some diatomic ionic molecules are given in Table 3.B.Interatomic Forces and Bondings in Solids 55 Table 3.B Bond lengths and bond energies of some diatomic ionic molecules Vill, CALCULATION OF LATTICE ENERGY OF IONIC CRYSTALS The lattice energy of an ionic solid will differ from the bond energy of diatomic ionic molecules since, in the former case there will be interactions between more than two ions. The cohesive energy of an ionic crystal is the energy that would be liberated by the formation of the crystal from individual neutral atoms. Cohesive energy is usually expressed in eV/atom, or eV/molecule or in ki/kmol. The bond energy of a molecule held together by an ionic bond is not the same as the cohesive energy of the crystal, because in the crystal each jon interacts with all the other ions present and not just with one, two or three of the opposite sign. Some- times the lattice energy, rather than the cohesive energy, is presented; the lattice energy is that energy evolved when a crystal is formed from individual ions, rather than from individual atoms. Let us now consider the case of NaC! which is one of the best examples of an ionic compound. Ionic crystals are strongly bound with binding energies (cohesive energies) of about 5—10 eV per molecule. This is the energy required to dissociate the lattice into positive and negative ions at infinite separation. Two common types of structures found in ionic crystals are NaCI structure which is face-centred cubic and CsCl which is body-centred cubic. The calculation of binding energy of ionic crystals generally requires a knowledge of forces acting between the constituent particles. In the classical Born-Madelung theory of ionic crystals, it is assumed that the electrons are transferred from electropositive atoms (Na, Ca, K, Mg) to electronegative atoms (O, F, Cl). The stability of an ionic crystal depends on the balancing of atleast three forces: the electrostatic, or Coulomb forces between the ions which give a resultant attraction falling off with the square of the distance; van der Waals forces of attraction diminishing according to the seventh power of the distance (usually neglected); and the interionic repulsive forces falling off still more rapidly with distance. The resultant of the attractive and repulsive forces is to lead to an equilibrium position of minimum potential energy; i.c.; of greatest stability as shown in Fig. 3.4. z For two ions of charges Z,e and Z,e separated by a distance r, the attractive energy is — ZOE and there: or eat et amegr’ anor’ 4megr fore this energy is. — trivalent, For the whole crystal, the Coulomb potential energy may be written as the net Coulomb potential energy of any one ion due to the presence of all other similar and dissimilar ions present in the crystal, The minus sign shows that the net Coulomb energy is attractive. The constant A is known as Madelung constant.4@ ‘You have either reached 3 page that is unavailable for viewing or reached your viewing limit for this book.4@ ‘You have either reached 3 page that is unavailable for viewing or reached your viewing limit for this book.4@ ‘You have either reached 3 page that is unavailable for viewing or reached your viewing limit for this book.Interatomic Forces and Bondings in Solids 59 2 energy of the sodium ion at A due to thees 6 CT ious is —2— eon Ie? 6? Ane V2r RE 2 respectively. Thus the Coulomb energy of this Na’ ion at A in the field of all other ions is ‘Similarly 12 Na* ions at ¥2r, and 6 Na’ ions at 2r, respectively contribute ya et MR Eo % Ane V2ry AN EyVIK MM EoIr é 2.8 6 | =~ Ae ot oe Omen aw For a kmol of the crystal, the total Coulomb energy is jae [o-2e tf ] men pew 3.18) The constant A is called Madelung constant and A = 1.75 for NaCl structure. Note that in equation (3.18) (Ze) (Ze) must be used for e and the quantity Z,Z, is one for monovalent alkali halides such as sodium chloride. The minus sign indicates that the average influence of all other ions on one ion under consider- ation is of an attractive nature. Crystal structure Madelung constant Sodium chloride 1.747558 Caesium chloride 1.762670 Zinc blende 1.6381 X. CALCULATION OF REPULSIVE EXPONENT FROM COMPRESSIBILITY DATA Born obtained the unknown repulsive exponent (n) from measurements of the compressibility of the crystal as follows: ‘The bulk modulus of the solid at absolute zero is given by ap AP) mie) ‘Thus compressibility is at 0K G19)60 Solid State Physics From the first law of thermodynamics dQ=dU+aw If the solid expands by dV against a pressure P due to the supply of dQ amount of heat, then aW = Pav dQ =dU+Pav Neglecting the thermal effects (dQ = 0 at very low temperatures), we write aU +PdV =0 ih Kaley [#4] 3.20) In sodium chloride structure the nearest neighbour distance r = 7q,+7y,= a/2 and the volume per molecule is. @'/4, Therefore the volume of a kmol of the solid is v[28] [Janeane 21) a 1 “) “sain (21a) i and hence compressibility at 0 K is given by 4 ‘Thus (Hea (AF) (a(S) ox At the equilibrium spacing r= and V=Vy=2Nyro (Refer eqn. (3.21) ‘Thus equation (3.22) becomes fu -[4] @u av Lav] aF.Interatomic Forces and Bondings in Solids 61 The equation (3.20) becomes v( 33) wav, ar \(d'u wma 1 | 2hors [3] 3.220 B 2 a! (aay From equation (3.12) At the equilibrium spacing, r = rp (refer equation 3.14) and Aer! B= an eyn aU Ae? n(n +B ful anit D8. oy (<2 _. Mines’ a en,| He pMas Dacre Mam eg a rg? 4m Ey 4meyrl 7 NyAe*(n 41-2) N,Ae? men men ap 4] Bt Me oot] 1 Ae -)) 3.23 a" Tam ey rh 023) (m=1) Equation (3.22a) is Kez Te €or ‘Thus (@-De Aep n= G24)62 Solid State Physics ‘The experimentally determined cohesive energy of NaCl crystal is 766 x 10? ki/Amol, or 7.95 eVimolecule. ‘The energy (U,) due to Coulomb attraction is 8.95 eV, taking rp = 0.281 nm for NaCl. Substituting these values in equation (3.15), we find n = 9.1. ‘The compressibility data for sodium chloride was measured by Slater at low temperatures and the extrapolated value at absolute zero was found to be 3.3 x 10°" m?/N, Substituting this value of B in equation (3.24) with ry = 0.281 nm and A = 1.748, we get n = 9.4, The small discrepancy between the experi determined value of 1 and the one calculated from equation (3.16) is due to a very small contribution from van der Waals forces to the total energy. Physical properties of some selected ionic crystals are given in Table 3.C. XI. THE BORN-HABER CYCLE The formation of NaCl molecule may be visualized as occurring in different steps, each of which results in energy absorption or evolution. An experimental check on the calculated values of the lattice energies may be obtained from Born-Haber cycle. Ne g0tg) a Se wo Gos? vy act Fig. 3.7 Born-Haber Cycle. ‘The Born-Haber cycle for NaCl crystal can be represented as follows: Those quantities that require the expenditure of energy are represented as positive and those that take place with the release of energy are represented as negative. The cycle can be as follows: (i) Initially we start with solid sodium and chlorine molecule. Solid sodium is vaporized by sub- Jecting the sublimation energy (S) while chlorine molecule is dissociated into its constituent atoms by supplying dissociation energy (D), DIZ is the dissociation energy per chlorine atom. (ii) ‘The outer electron of Na gaseous atom is removed by applying the ionisation energy (f) and this electron is added to C1 atom. As the chlorine has the clectron affinity £, an energy £ is given out. Gili) The two ions (Na’ + CI) are arranged in the lattice and hence the lastice energy (Us) is released. (iv) We again reach to the starting point by supplying an energy (AH) known as heat of dissaci- ation.Interatomic Forces and Bondings in Solids 63 S5S8S8 g & gee g <= oye GOL 1) tomyry wy KBszua any stesso oquoy owos jo sanuadosd fwoishyd 9 "C HEL4@ ‘You have either reached 3 page that is unavailable for viewing or reached your viewing limit for this book.dnteratomic Forces and Bondings in Solids 65 Reaction between ionic compounds in solution state is always fast. This is because in a solution, ionic substances exist as ions and chemical reactions take place between the ions. The ionic crystals are transpar- ent for all frequencies up to the value called the fundamental absorption frequency. At frequencies higher than this, they are opaque. High hardness and low conductivity are typical properties of these solids. When subjected to stresses, ionic crystals tend to cleave (break) along certain planes of atoms rather than to deform in a ductile fashion as metals do, Xl. EXAMPLES OF IONIC SOLIDS Sodium chioride, magnesium oxide, caesium chloride and potassium iodide. Lithium hydride and potassium oxide are other examples of ionic crystals. XIV. COVALENT BOND (a) G) G) The covalent bond is formed by shoring of pairs of valence electrons between like atoms rather than by electron transfer. A simple example of covalent bonding is found in the chlorine molecule. Here the outer shell of each atom possesses seven electrons. Each chlorine atom (b) would like to gain an electron, and thus form a stable octet. This can be done by sharing two electrons between pairs of chlorine atoms, thereby producing stable diatomic molecules. In other words, each atom contrib- utes one electron for the sharing process The simplest case of a single covalent bond occurs (ce) in the hydrogen molecule. The nature of the covalent bonding in this molecule can be demonstrated as follows: Fig. 3.8 Molecular orbital formation froms orbitals (a) two isolated atomic orbitals (b) overlap (c) the Consider the hydrogen molecule, H). When two isolated molecular orbital H atoms, each with its electron in the ground state 1s orbital approach each other, the 1s clouds begin to overlap. Each electron is attracted to the other nucleus ‘and the overlap increases (provided the electrons have opposite spin). The two atomic orbitals merge into a molecular orbital. Within the molecular orbital, the two electrons are attracted to both nuclei, When the tepulsive forces have been balanced the attractive forces a molecule results, having stability greater than that of the two isolated atoms. The covalent bonding is also known as homopolar or electron-pair bonding. It is the common type of bonding in organic molecules and in many inorganic molecules, In the molecular orbital of H,, the two electrons are equally shared between the nuclei and cannot be specifically identified with either nucleus. The two shared electrons are more likely to be found between the two nuclei and thus the electron density is relatively large The balance between the attractive and repulsive forces in hydrogen molecule occurs at a separation of 0.074 nm. Hence some energy must be spent to break the covalent bond in a hydrogen molecule into faydrogen atoms. About 4.5 eV is required to break one H—H bond. Thus H,+4.5eV > H+H4@ ‘You have either reached 3 page that is unavailable for viewing or reached your viewing limit for this book.Interatomic Forces and Bondings in Solids 617 Table 3.D Covalent bond lengths and associated binding energies Bond Bond length Binding energy Bond Bond length Binding fam) in kiAmol (am) anergy in (ini) kdmol Other examples are: NHN ——+ Ny ——» IN YNZ —+ N EN, lor) No 4 4 | C+ 2H, ——- CHy—e H CE Bowater 4 ”4@ ‘You have either reached 3 page that is unavailable for viewing or reached your viewing limit for this book.4@ ‘You have either reached 3 page that is unavailable for viewing or reached your viewing limit for this book.4@ ‘You have either reached 3 page that is unavailable for viewing or reached your viewing limit for this book.Interatomic Forces and Bondings in Solids 71 ‘Sheets of atoms can bond to each other by weak secondary bonds. These weak bonds have no valence requirements, The structure which results from bonding the sheets together is shown in Fig. 3.12, and is the flaky structure of graphite. Because the bonds holding the sheets together are weak, the sheets can readily TT) fb) “bbb aly »{t| wlth «(t] @ ) © Fig. 3.11 (A) (a) Carbon in the ground state (b) in the excited state (c) in the hybridized state. slide past each other. The ease of sliding accounts for the lubricating properties of graphite. Both diamond and graphite have the same chemical composition, but the manner in which the atoms are arranged has a vast effect on physical properties. The metallic orbital accounts from the fact that graphite is an electrical con- ductor while diamond is not. Graphite is used as ‘lead’ in pencils for its softness and as lubricant, for weak van der Waals forces between the sheets, in important applications. The following important points may also be noted in addition: o (i) (iii) ‘Attainment of octet configuration or noble gas configuration is not essential in covalent bond forma- tion. For example, in the case of borontrifluoride, each fluorine atom has a noble gas configuration, but the boron atoms has only six electrons in its outermost orbit. The paired elec'rons shared by two atoms should be of opposite spin. This rule is called the rule of ‘wo. Thus the two electrons forming the pair which is shared between the two atoms can occupy the available stable orbital in either atom without violating Pauli’s exclusion principle. Depending on whether the electron pairs are shared equally or unequally between the atoms, covalent bonds can be subdivided into non-polar and polar bonds respectively. For example, hydrogen to hydrogen bond during the formation of H, molecule is a non-polar covalent bond, since the electron pair is shared equally between the hydrogen atoms. Similarly chlorine to, chlorine bond is also a non-polar covalent bond. But in the case of hydrogen chloride, hydrogen to chtorine bond is a polar covalent bond since the electron pair is more shifted towards chlorine because of its high affinity (electronegativity) for electrons. This results in a slightly negatively charged (— 8) chlorine end and an equal positively charged (+8) hydrogen end, in the HCI molecule. XVill, PROPERTIES OF COVALENT COMPOUNDS (Covalent compounds are mostly gases and liquids,4@ ‘You have either reached 3 page that is unavailable for viewing or reached your viewing limit for this book.4@ ‘You have either reached 3 page that is unavailable for viewing or reached your viewing limit for this book.74 Solid State Physics result from either a transfer of electrons or from a sharing of electrons, secondary bonds do not generally involve the valence electrons at all. Secondary bonds are thase comparatively weak intermolecular bonds formed as a result of dipole attractions, the dipoles being formed as a result of the unbalanced distribution of electrons in asymmetrical molecules. Dipoles may be permanent as in the case of hydrogen fluoride and water molecules, or they may be temporary, as in the case of noble gases. The three types of intermolecular bonds are dispersion bonds; dipole bonds; and hydrogen bonds. (Positive) Metal io! (Negative) Electron cloud Fig. 3.13 Mctallic bonding. XXIL_ DISPERSION BONDS Bonds of first type are made possible largely because the electrons of adjacent atoms in a mol- ecule tend to repel each other. As the electrons revolve around their nuclei, they tend to keep in phase as illustrated in Fig. 3.14, for a hydrogen molecule. The result is that the molecule has a small fluctuating net charge on each end and acts as an oscillating dipole. The hydrogen molecule, illustrated in Fig. 3.14, is instantaneously charged. negatively on the right end and positively on the Fig. 3.14 Dispersion effect in a hydrogen molecule (HP), left. This fluctuating charge on one molecule showing momentary polarization, negative on the right, tends 10 interact with the fluctuating charge on a positive on the left. neighbouring molecule, resulting in a net attraction. The strength of the bond depends on the ease with which one atom can influence the other. Molecules of the inert gases, which consist of single atoms, are held together by dispersion forces when the gases are solidified.Interatomie Forces and Bondings in Solids 75 Atoms of noble gases, it is found, have little attraction for one another and with rare exceptions they remain monoatomic at ordinary temperatures. Only at extremely low temperatures, when thermal vibrations have been greatly reduced, do these gases condense. It is this condensation which makes it evident that there are weak interatomic attractions which pull the atoms together, This is what is known as van der Waals forces. A 8 i ia Gi) Fig. 8.15 Dispersion forces betwcen two atoms of argon Consider the case of two atoms of the noble gas, argon, in close proximity to each other. If the elec- tron clouds are evenly distributed as in Fig. 3.15 (i), then there wil! be no resultant displacement in either atom and they will neither attract nor repel each other. If, however, an uneven distribution of the electron clouds is present as in (ii), the atoms will repel each other, but if the electron clouds are distributed as in (iii), the electron cloud of atom A will be attracted by the ‘unprotected’ nucleus of the atom B. The displacement of the electrical charges necessary to produce a dipole is temporary and random so that a molecule, as a whole, over a period of time has no resultant dipole, However, if it has a displacement at any one instant it will induce another in a near by neighbour and a force of attraction will be set up between the two. It is thought that such interactions must be largely responsible for van der Waals bonding between non-polar atoms and molecules. XXItl. DIPOLE BONDS A molecule of the hydrogen chloride gas contains one atom of hydrogen and one atom of chlorine, cova- lently bonded (H—C1). In this covalent-bonded hydrogen chloride (HC!) molecule, the net effect of the ¢lectron-sharing process is to give the chlorine atom a slightly negative charge while the hydrogen atom has a corresponding positive charge. The magnitude of the charges are actually quite small, being 0.272 x 10”4@ ‘You have either reached 3 page that is unavailable for viewing or reached your viewing limit for this book.Interatomic Forces and Bondings in Solids 77 +OH Fig. 3.17 Hydrogen bond between two water molecules. Strong attractive forces between positive and negative ions (e) (a) Positive Shared valence jon electrons Centers of positive and ot ni charges seperated in each atom Fig. 3.18 The four types of chemical bonding in solides (a) Metallic bonding (b) Tonic bonding (c) Covalent bonding @ van der Waals bonding78 Solid State Physics 9 400 PATOs "208 "youlojeD “wosLy sainscjo woT Ase not -Teyskxo wry 00 29n -pyour woxy SAI N040.) spamoyoo so ouedsies, ‘AuQoNpUOD MO] “soyodip Bunusoy sojns9joui 204 -sou0 “m9 FN DV sayeasfe soynaojou trees ‘qreuowse290 20 sauoyy yr Jo asm oq sommes uray sop 18 1d29%9 MOLT suondaoxa ay 8 ye Kas Sypenscy caanpayar iy Ayan anpLoD pooR ‘suon po douaqe Jo JoquUME pets Bupany siuawaye soy, ‘pp "wneMLaD ‘puoURI “92°89 DN sanding somax8e s(n -2]0u) jyeurs £]peUCESTD90 40 stuOTY SWIORE 20 SIPHIIOU MMOWICT, aig anode A, wn ‘prerpounsa wrod Sanjay pood Ks Pood A139, aFes02i) areypowuzatuy ‘areipounzaquyy Rusu fad yy ‘san0]09 pood Jo ADUEA IPLAA snoqo.) “panouu Aiud ‘annaoyjan Kpuiiay ox aazedsuesy, 100116 “Ppamoyoo 0 waredstEa, ase] Ayanoapues jeauD9p> 807] Auansnpuoo mo] itananpuo peaunoai “depaso swore “suona9y9 a0u2yes yo raquinu (om) Jo spenque anuore uoyM, —_JOITEMIS SB SKOTE aNp JO DUO HOKLAA —_WOHEPUGD LOIRELLIO} PUG, pur ajodip 10} jeuonaasig Feuons2ip-00N Teaonpang raonsasp-woy poo Jo sais ALS ~ 12

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