CHAPTER 3 Quantum Physics 3.1 Introduction Prior {0 1900, the classical physies or the Newtonian mechanics seemed to explain most of the phenomena in physics such 1. Motion of mechanical objects—both on celestial and terrestrial scale 2. Discovery of electron by J.J. Thomson in 1897, assuming electron to behave as a Newtonian particle 3. Motion of molecules in gases Many physicists believed that, during this period, Newtonian mechanics would eventually be able to describe all the natural phenomena. Even the development of electrodynamics by Faraday and Maxwell seemed only to add new forces to the already known gravitational force, leaving Newton's laws untouched. However, towards the end of 19th century and the beginning of 20th century, cracks began to appear in physics. For example, Newtonian mechanics could not account for the motion of electrons going around a nucleus. In addition to this, even the following remained unexplained: Development of a suitable atomic model Discovery of X-rays and radioactivity Spectral distribution of thermal radiation from a black body Low-temperature specific heats of solids Appearance of only five degrees of freedom in motion of a free diatomic molecule at ordinary temperatures veeyr Thus classical physics was in Joss to explain physics at the atomic scale These could be understood only when Planck, in 1900, gave his quantum theory, according to which radiation energy was considered to be discrete or quantized rather than the existing concept of being continuous. The idea given by Planck could solve all the problems which the classical physics could not explain. Later, even Einstein used this quantum idea to explain the photoelectric effect. 67 Scanned with CamScanner68 Physics for Engineers This is how the ‘dual character of electromagnetic radiation’ came into being, according to which ‘electromagnetic radiation sometimes behaves as a wave and sometimes as a stream, of particles (i.e., quanta)’ At about the same time, the existence of discrete values for the measurable parameters of atomic systems also became apparent, through: Einstein's and Debye’s theories of the specific heats of solids Ritz’s classification of spectral lines Franck-Hertz experiment (for discrete energy levels) Stern—Gerlach experiment (showing that the component of magnetic moment of an atom along the external field has discrete values) eeNe Thus the physics of the first quarter of 20th century is based on the following two inferences: 1. The dual character of electromagnetic radiation 2. Existence of discrete values for physical quantities and, is now called the old quantum mechanics. ‘The ‘old quantum mechanics’ along with the third inference due to Prince Louis de Broglie (1924), that even ‘matier has dual character: particle-like and wave-like’, is called the new quantum mechanics or simply as quantum mechanics. 3.2. Black Body and Classical Theory of Radiation A prefect black body absorbs all the radiation incident on it and hence appears dark. The emission radiated by such a body is called a black body radiation, It is not easy to realise a black body. However, an enclosure provided with a small opening can be treated as a black body as the radiation entering such an enclosure through the small opening gets trapped in the enclosure and undergoes back and forth endlessly (as if it is absorbed completely) before it could get chance to come out of the opening, Such a body maintained at a desired (emperature constitutes a source of black body radiation, According to Kirchhoff, a black body is a good absorber as well as a good emitter or radiator. The emission from such a body depends only on the temperature it is raised to and not on its nature. Way back in 1893 to 1897, Lummer and Pringsheim carried out a series of researches on the black body radiation. A study of energy distribution in the spectrum of such a black body radiation (Figure 3.1) was done. Following classical laws, when applied to the black body radiation, led to wrong and inconsistent results not agreeing with the experimental data: 3.2.1 Stefan’s Law Stefan showed that the total energy density—the energy per unit volume due to different wavelengths put together in the spectrum—was directly proportional to 4th power of absolute temperature of the black body, ie., E = oT" (Stefan’s law) G1) where is the Stefan's constant and T is the absolute temperature. Scanned with CamScannerQuantum Physics 69 1910K 1s10K 1370K 1 Figure 3.1. Black body radiation. 3.2.2 Wien’s Law Wien clubbed his two laws, 2,,7-constant and ET~-constant, to develop the following empirical formula for monochromatic energy density E, within the black body maintained at a fixed temperature in the wavelength range A and A+ da: E,dazahSe"Tdd — (Wien's law) (3.2) where A is the wavelength corresponding to the absolute temperature 7, and a, and ay are the first and the second radiation constants. 3.2.3. Rayleigh-Jeans Law Lord Rayleigh derived the radiation distribution law more rigorously using the concept of modes associated with the electromagnetic radiation undergoing back and forth reflections inside a black body by the walls forming a system of standing waves for cach frequency present. Each mode of vibration has two degrees of freedom—one for potential energy of the oscillator and the other for its kinetic energy. The energy per degree of freedom being 4&7, the total mean energy per mode of vibration becomes kT (where k is the Boltzmann constant). The total number of modes of vibration, dN, per unit volume in the wavelength range A and T= A+ dA is aN, = 8raA 63) ‘The Rayleigh—Jeans law, which represents the total energy in the wavelength range A and 4+ dA, can be obtained simply multiplying Eq. (3.3) by AT, hence Eqda = aNy-kT = 8nAAKTAA or Eyd = 80kTIAA (3.30) Scanned with CamScanner70 Physics for Engineers 3.2.4 Failure of Classical Theory of Radiation 1. The total energy of radiation at a given temperature is equal to the area enclosed under the corresponding curve and the horizontal axis. With increase in temperature, this area is found to increase with 4th power of the absolute temperature. This verifies Stefan’s law. However, Stefan’s law is silent about energy distribution among different wavelengths. 2. With increase in temperature, the wavelength corresponding to the maximum, 2,,, energy shifts towards the shorter wavelength side. This verifies Wien’s displacement law Jnl’ = constant However, this law fails for longer wavelengths, and at infinite temperature, gives finite energy density contradicting the experimentally verified Stefan’s law. 3. Rayleigh-Jeans law holds only for longer wavelengths and, as A decreases, the energy radiated in a given wavelength range dA increases rapidly and achieves infinite value for very short wavelength—a result in contradiction with the experimental data (Fig. 3.1). This failure is often called ultraviolet catastrophe of classical physics. Conclusion: None of the classical laws could account for the black body spectrum completely. This resulted in the failure of ‘classical theory of radiation’. 3.3. Quantum Theory of Radiation On the failure of classical theory of radiation, Planck thought since the classical formulae were derived very carefully without any error, there must be some problem with the fundamental assumption made for their derivation that the energy changes of radiators take place continuously. So Planck gave his revolutionary idea that the ‘energy changes could happen only discontinuously and discretely, ic., the energy changes are an integral multiple of a small unit of energy, which he called quantum’. This idea gave birth to ‘quantum theory of radiation’, which could finally explain completely the experimental facts of black body radiation, 3.3.1. Planck’s Energy Distribution Law To derive his formula, Planck, in addition to his quantum idea, also assumed that energy of a radiator or an oscillator, E, is directly proportional to its frequency v. That's E = nhv, where h is a constant of proportionality and 7 is an integer having values 1, 2, 3, .... Further, applying laws of probability to these oscillators, Planck derived following formula for the average energy: iv Bae G4) elaT 1 where T is absolute temperature and & is the Boltzmann constant. To obtain energy density, Eq. (3.4) is multiplied by 874~dA—the number of resonating modes per unit volume lying ithin the wavelength range A and 2+ d&: Scanned with CamScannerQuantum Physics 71 M(c/A) c ely 89 Bd = 8a tga— = snd ah em] et “5, « yan th. 6s) tat 1 This is called Planck's energy distribution law. It explains the experimental data as per Figure 3.1 3.4 Derivation of Classical Formulae from Planck’s Law Wien‘s Formula For short wavelengths, e"”? becomes much greater than 1. Hence, Eq. (3.5) reduces to 8ahcd dd El a or E,dd=a aoe" dd (Wien’s formula) hc where ay = She and a; =—. Further, differentiating Planck’s formula (Eq. (3.5)] with respect to 4 and then equating it to zero, the Wien's displacement law, 2,7 = constant, can be obtained: d |8rhca~ da| efiT 1 or ca da te kar he or -sa[ -i}-x! a or a -i}ea[ "AT ae he hte or (# Jost eth Scanned with CamScanner72 Physics for Engineers he , eA, fe or ss are? he Potting z=, we get 8, T & S-2=5e* Solution of this equation is nearly 5, so putting z = 5 on right side for the exponential term only and then solving, we get z=497 he 97 Thus, aT a ra ie $:626 x 10Js x 3 x 10*ms™ o 497k 4.97 x 1.38 x 10° Jk Hence qT = constant ‘The value of the constant = 2.90 x 10 mK Rayleigh-Jeans Formula For long wavelengths, e”#7 becomes so small that in Eq. (3.5), (eT — 1) reduces to hclAKT, Hence 5 AKT Eydh = 8ahch* “dd=8nkTA “di (Rayleigh-Jeans formula) ic 3.5 Quantum Concept of Radiation: Postulates According to Planck, electromagnetic radiation is emitted as an integral multiple of a small unit of energy, called ‘quantun’; each quantum being of energy ty. The postulates of his theory are as follows: 1. Energy of an oscillator is quantized having energies, E = uh 66) where V is the frequency of the oscillator and = 1, 2, 3 2. Energy absorbed or radiated by an oscillator is quantized in steps of Hiv, ie., AE = (Amiv G.7) where An = 1, 2, 3, ... Scanned with CamScannerQuantum Physics 73 3.6 Discovery of Planck’s Constant According to Planck, energy E of an oscillator is directly proportional to its frequency ¥, ie., E=hy where his a constant of proportionality, and is named Planck's constant in Planck's honour. This constant states that ratio of energy of an oscillator to its frequency is always constant and is equal to 6.626 x 10 Js. 3.7. Applications of Quantum Theory of Radiation “Photoelectric effect’ and ‘Compton effect’ are the two important applications of the quantum theory of radiation. 3.7.1 Photoelectric Effect Photoelectric effect is the phenomenon of ‘emission of electrons from a metal surface when light is incident on In a photoelectric set up, two metal plates A and B are enclosed in an evacuated glass bulb, and the circuit is made as shown in Figure 3.2. The current flows if plate A is connected to negative of the battery. When plate A is connected to positive of the battery, electrons are reflected back by plate B and consequently no current flows. Following can be varied: intensity Tand frequency v of the incident light, the retarding potential V as well as the emitter itself. Current can flow only if the electrons have sufficient kinetic energy to overcome the retarding potential. The current so produced is called photoelectric current or photocurrent. Light e BI ales “et | 1 Figure 3.2 Photoelectric set up. Following results are observed: 1. The photocurrent i begins instantaneously in less than a nanosecond time and is independent of the intensity of light [Figure 3.3(a)]. Scanned with CamScanner74 Physics for Engineers 2. For a given frequency and voltage, the photocurrent increases proportionately with intensity of the incident light [Figure 3.3(b)] 3. For given frequency and intensity, the photocurrent decreases with increase in the retard potential and becomes zero for its certain maximum value called the stopping potential, V,, The stopping potential is independent of the intensity of light [Figure 3.3(c)], ie., 1 ae 3 vin =F 4, For a given emitter, the stopping potential increases with frequency v of the incident light as eV, = hv — w; work function w being constant. And for different emitters, w changes and so does stopping potential while slope remaining the same as fis a constant quantity [Figure 3.3(d)]. 5. To release an electron from a given emitter, the incident light of certain minimum frequency, vp called the threshold frequency is required. A photon carrying energy less than the threshold value will not be able to release even a least tightly bound electron, howsoever intense be the incident light [Figure 3.3(e)]. i 3 g zZ 2 = z = =| |= Time Intensity 7 Retarding potential, 0's @ o) © < 1 z 2 z 2 21 7 weequency, n g w/e Vuf Yoo Frequency, V wye @ © Figure 3.3 Graphical representation of experimental results. The classical theory of light can explain none of the above results except (2) that the photocurrent increases with intensity. Of course, more the intensity of incident light more the photons and more the ejected electrons and consequently more the photocurrent. Scanned with CamScannerQuantum Physics 75 Even the Planck's quantum theory of radiation, according to which radiation is composed of energy bundles only in the vicinity of the emitter, could not explain photoelectric effect To explain this effect, Einstein extended Planck’s idea and added that once quantum of energy was radiated, it preserved its quantum nature throughout its life. The quantum interpretation of light that light consists of photons explains all the above results from (1) to (5). According to this theory, energy of a photon is absorbed by a single electron, But keeping conservation laws of energy and momentum in mind, it is possible only when the electron is bound to the material. Thus (o release an electron from a material, certain minimum energy called the work function is required. The remaining energy of the incident photon is transferred to the released electron as its kinetic energy. Thus for a given material, the ejected electrons carry various kinetic energies varying from zero to maximum. ‘Thus, if a photon of energy /rv is incident on a material, the energy of the photon will be used in two steps (Figure 3.4): 1. To impart energy, equal to the work function w to an electron to release it, Using result (5), iff Vo is the threshold frequency, then w = ItVo, 2. To impart the released electron its remaining energy to give it the maximum kinetic Ls energy, "Vmax, WhEIE Viz 18 the corresponding maximum velocity. ‘Thus, 1 1 hyv=w+ zm =hyy + 3M and, using result (3), pr =e¥,, we get frm eV,=hv-hv, (Photoelectric effect) (3.8) Equation (3.8) is called Einstein’s photoelectric equation. Energy Lp? dn ve vs w=hvy Figure 3.4 Einstein’s photoelectric equation. Scanned with CamScanner76 Physics for Engineers The almost instantaneous absorption of a photon [result (1)] is also explained as the absorption of « photon happens without any time delay. Finally, more the intensity of incident light, more the photons, and hence more the ejected electrons and consequently more the photocurrent {result (2)] 3.7.2 Compton Effect In photoelectric effect, a photon gives all of its energy to an electron. This is possible only for bound electrons. On the other hand, with free electron what happens is called Compton effect. Here, whole of the photon energy /iv, does not get transferred (o the electron and, therefore, the photon gets scattered with longer wavelength 4. The electron recoils with momentum mv and energy mc? Considering a material particle (Figure 3.5), say, an electron at rest having zero momentum (p) =0) and energy equal to rest energy (£2 = myc’). It is hit by a photon. 7 Incident photon E=hv peso AY ’O pha (a) Before scattering (b) After scattering Figure 3.5. Compton scattering. ‘The conservation of kinetic energy is given as: Iv + gc? = hv! + me? or -S=me* - me? (3.9) For the conservation of the momentum along x-axis, we have Momentum before impact = Momentum after impact 4 +0=H cose + mveos0 (3.10) and along y-axis, we have A 0=s;sing — mvsind GD Scanned with CamScannerQuantum Physics 77 In fact, we are (o develop an expression for in terms of the scattering angle 9. And for this, we proceed as under: Rearranging and squaring Eqs. (3.10) and (3.11), we get 2 (mvcos6)? (4 Kcose) ewe 2K? cos 242 cos? 2 my? cos’ Ona noes o- We (3.12) 2y2 in? aa sin? 3.13 mv? sin? O= sin? @ (3.13) Adding Eqs. (3.12) and (3.13), we get 2 mye 4 G14) Now, relativistic mass is given as: (3.15) ‘Squaring and simplifying Eq. @.15), we get my" = c*(m? — ma) (3.16) Equating Eqs. (3.15) and (3.16), we have em -m=r( (3.17) Solving Eq. (3.9) for mt and then squaring, we get m=m +t oN cA cat Hence or (3.18) To eliminate mass of electron, compare Eqs. (3.17) and (3.18), we get J =0(s J - tas) wre Fa Scanned with CamScanner7B Physics for Engineers or or or or Hence AL= a —cos@) (Compton effect) (3.19) mee nt (3.19) is the relation between wavelength of the incident photon 2 and the angle through which the photon scatters ¢—the desired expression for Compton scattering. The term mec in the expression is called the Compton wavelength. Its value for electron is 0.0243 A The shift in wavelength depends upon the scattering angle @ and is independent of the incident photon’s energy. 3.8 Wave-Particle Duality The electromagnetic (¢.m.) radiations have two aspects: wave and particle, The interference and the diffraction of e.m. radiations can be explained if the radiations are considered to be consisting of waves. The distinctly quantum effects of e.m. radiations such as photoelectric and Compton effects can be explained only if the light is assumed to consist of particles such as photons. Each photon with an energy £ and momentum p is respectively specified by frequency (v) and wavelength (A) of radiation as under: £ 3.20) vet 2 h aes G2) P as E = pe for photons being zero rest mass particles. ‘The quantities, v and A, which have most distinctive wave properties, appear on the left hand side of Eqs. (3.20) and (3.21), while E and p having most distinctive particle properties appear on the right hand side of these equations. Thus the wave-particle duality of e.m. radiations is implied in these equations. The fundamental constant of quantum theory it relates the particle characteristics to the wave characteristics, Thus, we can say (hat electromagnetic radiations will, under some circumstances, behave as particles, or that photons—the zero rest mass particles will, under some circumstances, behave as waves. Prince Louis de Broglie (1924) conjectured that because of the symmetry of nature a material Je as well can exhibit wave properties called the de Broglie hypothesis and, therefore, part Scanned with CamScannerQuantum Physics 79 Eqs. (3.20) and (3.21) have greater generality and apply to both the finite as well as the zero rest mass particles. However, the attention is focussed on the second equation (Eq. (3.21)], as wavelength can be measured from interference and diffraction effects. Equation (3.21), when applied to a wave associated with a finite mass (material) particle, the relation is called the de Broglie relation and the wave, a de Broglie wave—also called a matter or a pilot wave. The wavelength A of a material particle is called the de Broglie wavelength and p = mv is its momentum where m is the relativistic mass of the particle and v is the velocity 3.9 Bragg’s Law Crystals being in a 3-D arrangement of periodic arrays of atoms form a grating-like structure of parallel planes. Such crystals ean cause X-ray diffraction as their inter-planar spacing is of the order of X-ray wavelength, i.e., about 1A to 4A. Diffraction by 3-D crystal gratings requires rigorous consideration. However, Bragg (1913), a3 discussed below, simplified this problem by showing that diffraction by crystals is equivalent to symmetrical reflection from various Bragg planes. Each electron in the crystal atoms scatter the incident X-rays in all directions. Only those directions are of interest in which the X-rays scatter in phase with each other, i.e., they form a common reflected wavefront M’N’. This is possible only when the X-rays reflected from different planes have path length (Figure 3.6): AB + BC = d sin @ + d sin @ = 2d sin O is equal to an integral multiple of the wavelength of X-rays A, ie., 2d sin = nd 3.22) where n= 0, 1, 2, 3, interfere constructively. The relation given by Eq. (3.22) is called the Bragg’s Inw. d is the inter-planar spacing and @ is the glancing angle. Such rays Incident Sy wieliont Reflected wavefront Incident X-rays Bragg planes Figure 3.6 Diffraction from Bragg planes. Scanned with CamScanner80 Physics for Engineers The Bragg’s diffraction is also called Bragg’s reflection as the scattered rays (Figure 3.6) are parallel and make the same angle @ with the lattice planes as the incident X-rays. 3.10 Relation between Interatomic Separation and Scattering Angle Let an electron beam incident normally on a nickel erystal cut parallel to the principal Bragg planes, and the maximum intensity peak is observed corresponding to the scattering angle 50° Consider Figure 3.7 as glancing angle @ and 9/2 are complementary, @ + 9/2 = 90° =90° - 2 or a= 90° - 5 or sin = cos 3.23) Figure 3.7. Relation between D and ¢. From Figure 3.7, we have d=D sin (24) where. D = interatomic separation d= interplanar separation scattering angle Substituting results of Eqs. (3.23) and (3.24) in Bragg’s law, 2d sin@ = nA, we get g 2p sin& cosd = nd or D sing=nd (3.25) Scanned with CamScannerQuantum Physics 81 3.11 Davisson and Germer Experiment CJ. Davisson and L.H. Germer performed the first experiment (Figure 3.8) to observe electron diffraction, wherein they directed an electron beam, accelerated through 54 V, at a glancing angle (an angle complement to the angle of incidence) 65° at a nickel crystal having interplanar spacing, 0.91 A. ‘The scattered electrons were found to have a maximum intensity peak corresponding to the scattering angle 50° (Figure 3.9). | 1 Electron gun la = — Incident electron beam Electron detector LI interplanar separation D= Intertomie separation Brage’s “1 P planes “al Nickel crystal Figure 3.8 Davisson-Germer electron diffraction set up. Direction of incident beam Figure 3.9 Graph between intensity of seatlered beam and seattering angle at 54 eV. Thus for n = 1, the wavelength of electrons 4, corresponding to the constructive superposition at the glancing angle @ = 65°, was found by using Bragg’s law: 2d sin = nA, or 2x 0.91 A x sin 65°= 1.65 A (3.26) Scanned with CamScanner82. Physics for Engineers The de Broglie wavelength of 54 eV is given by the relation: 12.26 A 12.26A [¥ (in volt) $4 Gin volt) ‘The two wavelengths [obtained from Eqs. (3.26) and (3.27)] do not tally. This is precisely due to the fact that when the electrons enter the crystal, a work equal to the work function energy (1.3 eV) of the nickel crystal is done on the electrons making its total energy equal to 55.3 cV (as an electron accelerated through a potential of 54 volt acquires energy of 54 eV) and, therefore, the de Broglie wavelength becomes 7A (3.27) (3.28) Now, the de Broglie wavelengths measured by Eqs. (3.26) and (3.28) tally, verifying the de Broglie hypothesis. Note 1 de Broglie wavelength can also be found with the knowledge of the inter-atomie spacing and the scattering angle, which for nickel, are, respectively, 2.15 A and 50°, Dsing=nd or 2.15 A x sin 50° = 1.65 A (3.29) The same wavelength is same as obtained in Eq. (3.26), Note 2 Shortly after the Davisson and Germer experiment, G.P. Thomson, in 1927, studied the transmission of 15 keV electron beam through a thin gold foil, and observed circular diffraction patterns, confirming further the de Broglie hypothesis. Interestingly, G.P. Thomson was the son of JJ. Thomson who, in 1897, established the particle nature of electrons, using his cathode-ray experiment. For this, J.J. Thomson won Nobel prize in 1906. G.P. Thomson received Nobel prize in 1937 for establishing the wave nature of electrons, which he shared with Davisson for his electron diffraction experiment. 3.12 Electron Microscope The electron microscope is based on the principle of material particles exhibiting wave properties (de Broglie hypothesis). The material particles employed in an electron microscope are electrons because the wavelength associated with them (ic., de Broglie wavelength) is much shorter (than visible light; some 10° times shorter!). This is always preferred because the resolving power of an instrument is inversely proportional to the wavelength of the source. An electron microscope consists of an electron gun and an assembly of magnetic lenses—condenscr, objective, and projector lenses—all enclosed in an evacuated vertical tube (Figure 3.10). Unlike optical microscope, in an electron microscope multi used. The magnetic lenses are, in fact, (direct) current-carrying coils surrounded by soft iron, except for a narrow gap in the bore. The focal length can be varied by adjusting current; whereas Scanned with CamScannerQuantum Physics 83 (J Ja Btectron gun Anode plate —»— | — First condenser lens Second condenser lens Objective lens First projector lens ~ Image plane ‘Second projector lens Fluorescent sereen Camera Figure 3.10 Basics of an electron microscope. in optical microscope, the lenses (having fixed focal length) have to be moved to change the focal length. The condenser collimates the electron beam and illuminates the specimen placed in the bore of the objective lens. The objective lens magnifies the image up to about 40x in the object plane of the first projector lens. The projector lens, in turn, magnifies this image further in the object plane of the second projector lens, and the second projector lens magnifies this image up to 100000x on the fluorescent screen, where it can also be photographed. get 12.26 A mv \/V (in volt Taking extreme care, like using ultraviolet line of mercury (A = 25.37 A), oil immersion optics (numerical aperture = 1.4), quartz lenses and microphotography, the best resolution achieved with optical microscopes is only 1100 A. Scanned with CamScanner84 Physics for Engineers Whereas in an electron microscope, the electron gun normally operates between 50 to 100 kV. The de Broglie wavelength achieved varies from 0.055 to 0.039 A. But, because of the fact that magnetic lenses are more prone to spherical and chromatic aberrations than glass lenses, the limit of resolution for the electron microscope is limited to about 2 A 3.13 Wave Group ‘The concept of wave-particle duality is still difficult to conceive. This is so because unlike a particle, a wave cannot be confined to a point. For a particle having dual character, particle and wave, it is really difficult to accept how the wave extended over a region of space does not conflict with the particle located at a specific position. This conflict can be resolved by forming a wave group—also called a wave packet. A wave with same amplitude and wavelength and extending from x = —2 to +2 is represented by the equation: y = A sin(@r — kx). Such a wave is called an ideal wave train In reality, no wave train is of infinite extensions. The wave trains of finite lengths are called wave groups or wave packets. The resultant of two infinitely long waves of slightly different frequencies will be a wave comprising infinite number of wave groups extending from to +2, These groups move in +x direction with a velocity vg, called the group velocity. With increase in the number of waves (of slightly different frequencies), the wave group size decreases, and the separation between consecutive wave groups increases. The superposition of infinite number of such waves cancel each other everywhere except in the one localized region, thereby resulting in a single wave group (Figure 3.11), xe _,_ Wave group Figure 3.11 A wave group. If the wave group represents a particle, then the group velocity is equal to the particle velocity. This can be shown as under: Consider resultant of two phase waves: yi =A sin(@t— kx) andy) = A sin(@yt — kx), we have Y=y1 + y2 =A sin(@yr - kx) + A sin(@,r - kx) = 2A sin p[ Sot t =Coat— hs) Aste 22m [er teon = | 2 = 2A sin [(@, + @,) ~ (ky + kx) 085 10 = Oy - (hy +k] B30) int 2 Scanned with CamScanner‘Quantum Physics As the wave numbers and frequencies differ only by differential amounts, we have @,- = do ky — ky = dk 1 iO + 0) = 0 and dy + =k ath + ke) =k and thus Eq. (3.30) becomes y=2A cos 5 (te 1 = dk 3x) sin(os - kx) Thus the resultant is similar to the original wave with amplitude 2A cos (deo t dk ns oos( 221 &,) 2 2° 2 Having velocity of propagation, ie., do Group velocity v, = “2 up velocity », = SP Further, Particle velocity v= 2 pe m ome’ E 2n_2n _2np nl 2n_ 2m _ imp m 2 hp h 2nE and w= any te Using at and E = hv h Substituting values of k and co from Eqs. (3.34) and (3.35) in Eq. (3.32), we have do _dE », OE sdk dp From relativistic energy-momentum relation, we have Bape+ me On differenti ion, we get 2EdE = 2pe*dp or. oo Comparing Eqs. (3.33) and (3.37), we have 85 (3.31) (3.32) (3.33) (3.34) (3.35) (3.36) (37) Scanned with CamScanner86 Physics for Engineers which on comparison with Eq. (3.36), gives vg=v ‘That is, the group velocity (of the de Broglie wave group associated with the moving particle) is equal to the (classical) velocity of the particle. The phase (or wave) velocity is the velocity of the component waves superimposing to make the wave group; whereas, the group velocity is the velocity at which the energy actually travels. Also, as , hh) _{ me? \(h Phase (or wave) velocity «= va=(—]/+]=|"2 |(— |- (3.38) Wp) a mw) As v c, thus phase velocity associated with the waves is greater than the velocity of light. 3.14 Heisenberg Uncertainty Principle The size of the wave group Ax decides the uncertainty in the location of the particle, In a small size wave group, the particle position is precise but the wavelength is quite uncertain due to the presence of a few or just one wave. This uncertainty in wavelength A leads to uncertainty in the momentum (A= my), And this results in a broad range of momentum values on taking large number of momentum measurements. On the other hand, in case of a large wave group, due to the presence of large number of waves, the 2 measurement becomes more precise and, so does the momentum. But location of the particle becomes quite uncertain. Thus comes into force the principle of uncertainty, according to which both position and momentum of a particle simultaneously cannot be measured precisely. That is, ‘preciseness in one is at the cost of the other.” Thus a wave group of infinite size will have infinite precision (or zero uncertainty, ie., Ap = 0) in the measurement of its momentum and zero precision (or infinite uncertainty, ic., Ax =<) in the location of the particle and vice versa. Thus to reduce uncertainty in particle’s location, we need to decrease the size of the wave group. This is represented by the uncertainty relation, 1 Akax 2 > (3.39) where = 2nphh. Similarly, the uncertainty relation between frequency and time is given as: (3.40) Differentiating k = 2np/h, we have Scanned with CamScannerQuantum Physics 87 and, therefore, Eq. (3.39) becomes a” Axe 1 an A or Ap Ares G41) Equation (3.41) represents impossibility (o measure simultaneously and with infinite precision: both momentum and the corresponding position of particle or a photon. Equation (3.41) represents the first formulation of Heisenberg’s uncertainty principle, according to which the product of uncertainties in the position and momentum is equal to or greater than 7/2. Both position and momentum are to be measured along the same direction Similarly, using @ = 2nv = 2nE/h, and hence Aw = 24AEMh = AEth, Eq. (3.40) gives AE Ate A no 2 Equation (3.42) represents the second formulation of Heisenberg’s uncertainty principle, according to which the product of uncertainties in the energy and time is equal to or greater than N/2. or agar>” (3.42) Thus a precise calculation based on the concept of wave groups demands the product of uncertainties to be >A/2. ‘Thus according to the Heisenberg’s uncertainty principle, there are fundamental restrictions on the certainty of measurements of momentum and position [Eq. (3.41)] and energy and time (Eq. (3.42)]. Consideration of uncertainty is significant only in the microscopic domain (where the wave-particle duality is important) and not in the macroscopic domain. 3.14.1 Applications (or Consequences) of Uncertainty Principle Electrons cannot exist in a nucleus If an electron exists in a nucleus, then the uncertainty in the measurement of its momentum i h Ax >= Apan2s an or p> ls LO5dxc10™* 35 2Ax 2x5x107m 21.054 x10°kg ms! As the momentum p of the electron, inside the nucleus, must be of the order of Ap, hence Kinetic energy of such an electron = (Ap)c = pe = 1.054 x 10-7? kg ms“! x 3 x 10° ms = 20.6 x 10° eV = 20.6 MeV Scanned with CamScanner88 Physics for Engineers This energy is exorbitant, Even an electron associated with an unstable atom is known to possess only a small fraction of this energy. Thus existence of an electron in a nucleus is not possible. Broadening of spectral lines An excited atom emits a photon with a characteristic frequency (corresponding to its excess energy). The photon energy is uncertain by an amount given as: scare? 2 fh 1.054 x 104s or AE > pS 2A 2x10 where 10 s is the time spent between excitation of the atom and emission of the photon, The corresponding uncertainty in the measurement of frequency of the emitted photon can be found by differentiating the expression for photon energy E = iv, as AE = hav 5.27x 1075 6.63410 Js, ‘Thus the frequency of an emitted photon will have an uncertainty of atleast 7.94 x 10° Hz. Thus a photon (corresponding to red visible light) of frequency, say 4 x 10" Hz, will not appear to have precisely this frequency, rather it will be found to have a broadening of the spectral line by 25.27x1077J or 27.94 x 105 Hz 6 AV _7.94x10°HE 4s vo 4x10" Hz Uncertainty in energy measurement The uncertainty in particle’s energy depends upon the time spent on its measurement. An energy measured over large time-interval will have minimum uncertainty. For example, an electron in an atom spends most of the time in the ground state, therefore, Ar =e, and hence AE = 0, ie., it is well measured. Whereas, the electrons in the excited state are short lived, and thus have large uncertainty in AE. 3.15 Schrédinger Wave Equation In 1926, Erwin Schrédinger, the Austrian theoretical physicist, for the first time formulated an equation to find the wave function associated with a moving particle. This wave function can provide all the requisite information about the given particle. Scanned with CamScannerQuantum Physics 89 3.15.1 Time-dependent Schrédinger Wave Equation For a material particle moving with a speed v, not comparable with the velocity of light, the total energy of the material particle is given by Total energy (E) = Kinetic energy (3m) + Potential energy (V) E Thus writing a wave equation for a wave amplitude (function) ¥, eo Ev=P weyy (3.43) 2m W along x-axis can be specified by = Aertorks ‘As ¥ is like y in the wave equation y = a sin(ot ~ kx), but with a difference that the former is a complex quantity and the latter one, real and measurable, thes —s) o Wede? As Lamy = hv = B and nk = 2% Qn aah or wy = Aetimer-po a Differentiating Eq. (3.44) with respect to %, we have ay di (3.44a) (3.44b) Scanned with CamScanner90 Physics for Engineers Substituting the values of EY (Eq. (3.44a)] and p*¥ [Eq. (3.44b)] in Eq. (3.43), we get pe ae na -* dt 2m dx? Equation (3.45) is 1-D time-dependent Schrédinger wave equation. In 3-D, it is written as: +0 (3.45) (3.46) where Vea Sty (3.47) 3.15.2 Time-independent or Steady-state Schrédinger Wave Equation To transform Eq. (3.45) into a time-independent or steady state equation, write Eq. (3.44) as: wp = folio gibitoe (-iBiny. v=ve G.48) where y= Ae is a x-dependent wavefunction. Substituting the value of Y from Eq. (3.48) into Eq. (3.45), we get d rd de ism) 2d 0 icine (em nF (yee™) = (yer) +7 (yer™”) 2 yp usm) (HE) PP dV (ein) 4 v (yeitme or inlye If 2) Sor gee le CeIn) + (yee) iE vw dy ny)(—=) = -2 S¥ oy, or i wn ) Om de wy) w dy ny= 24% oy, or Vom ae 7) P Py 24 eer. or sweat ey 3.49) where Eq, (3.49) is a L-D time-independent or steady state Schrédinger wave equation. 2y fy? 2 For a 3-D system, we write fy + dy fy or V’yin place of “¥ in Eqs. (3.49) dv dy de dy where V is the potential energy and a function of x, y, ¢ and ¢ is affected by any restrictions on the system, A system can exist in a steady state only if the wave function and its derivative are continuous, finite, and single-valued. And to solve Schrdinger wave equation for a given system means to find the wave function associated with it. Scanned with CamScanner3.16 3.17 » 3.18 Quantum Physics 91 Postulates of Quantum Mechanics Wave function contains the entire information about a given system. Information regarding a system’s variable can be extracted from its wave function by using corresponding operator. Expectation value of a variable x of a system having wave function yis given by j ywoxyde . As probability cannot be determined for a single particle, we consider a distinctive system with a distinct number of possible results, cach having a certain probability. The average or the expectation value for position is given by Unnormalised or Normalised (3.57) Scanned with CamScanner94 Physics for Engineers Outside the atomic domain, ¥ and are practically equal. There is hardly any difference between them. But in the atomic domain, the uncertainty principle has to be satisfied. So, to find the expectation value, we first write the average of the positions of N’ particles uted along x-axis such that Ny are at x, Np at x5, Ns, at ts, .... 80 on. dis (3.58) To understand the expectation value quantitatively, let us consider a dice. On being tossed, the probability of getting the face with digit 1 is 1/6 and any of the face with digit 2 to 6, the probability is 5/6. In Eq. (3.58), ¥ stands for the value of toss, which is 1 for digit 1, and for any of the digits from 2 to 6, it is 5. The average of N tosses is given as: 2 ENA ON +N, Sy, N +N, T where N, and N2 are respectively the probabilities of getting the face with digit 1, i., 1/6 and the face with any of the digits 2 to 6, it is 5/6. ‘Thus the expectation value is given as: 1 5 OFO2 43 L. The problem is now reduced in finding y within the box between x = 0 and x = L. The Schrédinger wave equation is used to find y. The I-D steady-state Schrodinger wave equation (Eq. (3.49)] within the box reduces to 2 Wa. py =0 2m dx? a or +S Ey (3.59) dc or (3.60) where (3.61) The possible solution of Eq. (3.60) is YHA sinks + B coskx (3.62) Atx = 0, Eq, (3.62) becomes 0 =A sin@) + B cos) Hence B = and ye sinkx (3.62) As required, it will always give y= 0 at x = 0, since sinO = 0. But y= 0 at x = Z only when AL = nt where n = 1,2, 3, .. (3.63) Substituting for k in Eq. (3.61), we get nw) _ 2m wn? |) =Se o £,=— (3.64) ( L ) w 2mi? Scanned with CamScanner96 Physics for Engineers where n = 1, 2,3, ... is am integer, called the quantum number, Equation (3.64) shows that the ‘particle in a box’ can have only the discrete energies, called the ‘energy eigenvalues’ corresponding to » = 1, 2, 3, ... . Thus, unlike in classical physics, in quantum physics, the minimum energy corresponds to n = 1, ie., not zero as in case of classical physics. Such an energy is called the zero point energy. Now, substituting for k from Eq. (3.63) in Eq. (3.62A), the corresponding wave functions, called the eigenfunctions for the corresponding eigenvalues E,, are given by Wy =A sinky = A sin “ (3.65) These eigenfunctions, for each value of are single valued functions of x. And yj, and its derivative dy,/dx are finite and continuous everywhere within the box except at the end of the box. To find the constant A, Eq. (3.62) is normalised as: Jivatae =1 1 Thus 2 fai ("Ja =1 L ° ar or or or or (3.66) Vn & TE where n= 1, 2, 3, (3.67) The first three energy levels as well as the wave functions and the probability densities are plotted respectively in Figures 3.13 and 3.14(a) and (b) rere 2mv? Energy levels: £, = Scanned with CamScanner