MATTER WAVES UNCERTAINTY PRINCIPLE 2.1, THE OLD QUANTUM THEORY The work of Planck or black body radiation, photo-electric effect, Compton effect and variation ‘specific heat at low temperature is nee called old quantum theory. However, only after Rutherford, discovery that an atom consists of central massive positively charged core called nucleus surrounde by electrons could the theory be applied to a quantitative description of atoms. Bohr-Sommerfeld quantization rule ‘ In 1913, Bohr postulated the model of atom that @ Anatom consists of central massive positively charged core called nucleus surrounded by electron revolving in certain stationary states or quantized states} each corresponds to a definite energy and the h angular momentum of the electron is integral multiple of 5. (ii) The transition from one energy stote to another are accompanied by the gain or loss of energy equal to the energy difference between two states. To explain fine structures of hydrogen, the spectra of diatomic molecules and other such problems, Sommerfeld introduced a postulate that she momenta associated with both the coordinates (r.) (Fig 2.1) extended over one period of the motion is integral multiple of h. Practical difficulties The old quantum theory encountered practical difficulties in several different respects. (It could not be applied to aperiodic systems. (ii)_ It provided only a qualitative and incomplete treatment of the intensities of spectral lines. (ii) It could not explain satisfactorily the phenomenon of dispersions of light. Fig. 24 (iv). The old quantum theory gave incorrect results, when applied to rotational spectra of some diatomic molecules. Jn 1923, Neil Bohr tried to use classical theory asa limiting case of quantum theory by initroducing Bohr’s correspondence principle and achieved some success but ultimately old quantum theory could not explain all the properties of atomic systems. Conceptual difficulties. Apart from the practical diffculties as stated above, the old quantum theory failed ee conceptually satisfactory account of the fundamental phenomena, eee olor @ The old quantum theory could-explain the hypothetical assumption of Bohr that in stationatY orbits, electrons do not radiate energy as it was based only on empirical observation, and had no theoretical justification. (Gi)_Tecould not explain the processes connected with the spin of the electrons and Pauli's exclusion rinciple. a (iii) ‘The mechanism of emission and absorption of radiation in transitions was obscure. , (iv) The assumption of a dual character for light seemed to be self-contradictory. aa between stationary statesyarTeR WAVES AND UNCERTAINTY PRINCIPLE —Quantum-mechanical view point. a 1925, a new conce] i i ernis hypothesis cept was inroduced by de-Broglie and then by Schrodinger. de-Brogi Ser Cave A ate Tae eee erarenend sa ecoatcn such con ae ase mater waves. A lage numberof anomalies were explained systematically onthe basis Gaul complex problems i ions and material" particles. A satisfactory explanation was gi may ae in wave mechanical theories. The scope of quantum theory has been further extended in recent years and it has beer! ployed to understand the relativistic rant i funds of fields and their interaction with particle. etic mechanics and various 2.2. WAVE PROPERTIES OF PARTICLES The successful explanation of the Compton and i i The s an photoelectric effects and the experimental ee of the predictions made on the basis of these explanations, established it beyond doubt that electromagnetic radiation travels not in the form of a continuous stream of energy but in the form of tiny packets or bundles of energy, following each other in quick succession. These packets of energy were called photons that behave almost exactly like a material particle. On the other hand, the phenomenon like interference or diffraction of light or X-rays could not be explained unless electromagnetic radiation were assumed to possess a wave character. This resulted in the acceptance of the dual character of radiation, which is maintained till the present day. When radiation interacts with matter it exhibits its particle character ‘whereas when radiation interacts with radiation, it exhibits wave character. Radiation never exhibit both the characters simultaneously. ‘An interesting outcome of the acceptance of duality in the character of e.m. radiation was the hypothesis put forward by L.de-Broglie in 1924..He was guided by the following reasonings : 1. Nature is symmetrical 2. Our observable universe is totally composed of light and matter and light has dual character. 3. ‘There is a close parallelism between principle of least action in mechanics and principle of least time (Fermat’s principle) in optics. . DE-BROGLIE HYPOTHESIS ‘According to de-Broglie; “the wave-particle dualism should not be confined to radiation alone, but should also be extended to all the fundamental entities of physics”. The electrons; protons; atoms and snolecules, when in motion, should have some tyPe ‘of wave motion associated with them. de-Broglie root ce this hypothesis from considerations based upon the special theory of relativity and quantum theory. The waves associated with moving ‘particles are called matter waves or pilot waves or de- Broglie waves. ‘Expression for de-Broglie wavelength For Photon Energy of a photon can be written as B =e Xt ame 7" If a photon possesses some ‘mass (which by virtue of its motion i. its rest mass would be zero) its energy according to the theory of relativity energy of photon E. = (mass of photon) c? Using Eq. (2-1), we get 5 he a " (mass of photon)c? heh Ac he " mass of photon38 MODERN’S ATOMIC AND MOLECULAR PHYSICS (B.Sc. 1) 4 ‘So momentum of photon, p= (mass of photon) c ra he iat] Prt tw or a ela or awh ww(2.2) P For a material particle {finstead of photon, we consider a material particle of mass m moving with velocity , then momentum of material particle P= mv wavelength associated with the material particle, eee vwn(2.3) pmo This wavelength is called de-Broglie wavelength and the wave is called de-Broglie wave or matter wave. Characteristics of de-Broglie wave (D,_ The wavelength of de-Broglie wave is independent of the charge of the particle. Gd Slower the particle of a given mass, larger is its de-Broglie wavelength, (ii) Heavier the particle, lesser is its de-Broglie wavelength, 2.4. DE-BROGLIE WAVELENGTH IN TERMS OF ENERGY AND TEMPERATURE In terms of energy ‘The kinetic energy of a material particle of mass m moving with velocity v is given by 252 2 samt = MU LP Be om om ~ or P= J2mE of) » De-Broglie wavelength in terms of energy will be h_ok ; ate 2 ? VamE 2 In terms of temperature From kinetic theory of gases, the average K.E. of material particle is given by Es Sur So Eq. (2) becomes As + mS KT h or Ase --@)MATTER WAVES AND UNCERTAINTY BRINGIPLE: 30 2.5. DE-BROGLIE WAVELENGTH ASSOCIATED WITH AN ELECTRON IN A POTENTIAL DIFFERENCE OF V VOLTS F Let an electron having charge e and mass m accelerated through a potential V volts, and attains a velocity v. Kinetic energy of electron . . E= jv? - wn) Also, kinetic energy of electron is given by E=eV . voli) From (i) and (ii), we have yu? a or mu? = 2eV a. or mv? = 2meV or mv = JimeV +. de-Broglie wavelength of electron a2 tet ed Pp mv f2meV 6-62 x 10-4 or A= 2 x 9-1 x 1972! x 16x 10-9 VV 12-27 «107! _ 12-27 As m A (23) or Be (2.3) i VELOCITY OF DE-BROGLIE WAVES (Phase Velocity) We associate de Broglie wave with a moving particle, so it is reasonable to expect that this wave travels with the same velocity as that of the particle. If we call the de-Broglie wave. velocity as W, we may apply the usual formula W.= yA,to determine the value of W. The wavelength 4 is the de-Broglie wavelength given by = aes. mv Now from the Planck’s Law E = hyve = en(1) Also from mass energy relation E = mc? w=(2) From Eq. (1) & (2), we have mc? y wi de-Broglie wave velocity, is therefore, given by 2 h ewe = Wew a x e|%0 MODERN'SIATONIC AND MOLECULAR PHYSICS (8. Since the particle velocity v, must be less than the velocity of fight c, . Ww ie, de-Broglie waves travel faster than velocity of light. Siith a situation can be visualised in ca of electromagnetic waves e.g. velocity of X-rays in different rystals and that of sodium light in sodiun crystal is more than c. a: WAVE PACKET (Physical Me 8) < De-Broglie wave associated with a material particle has velocity more than the velocity of the particle Soit was difficult to conceive as tohow the de-Broglie wave was associated with the particle, Schrodinger Postulated that a moving particle is not associated with one wave but a group of waves called wave. packet, and cach wave has slightly different speed and wavelength. The wave packet is the result ofa superposition of individual sraues whose interference with one anther cesults inthe variation of amplitude “That defines the group shape,Since the wave speed varies with wavelength hence the different individual, 7K Fig. 2.2 Wave packet waves do not proceed together and the wave packet has speed different from that of the waves which compose it. The amplitude of each wave is sq.chosen that they interfere constructively over a sniall region of space as shown in fig. 2.2. The velocity of wave packet when calculated comes out to be equal to velocity of the material particle with which it is associated. Thus wave packet is a type of wave motion in which amplitude of the wave is very Jarge.in a. small region and negligible small in the rest of space. The probability of finding the pasticle is maximum where amplitude of the waves is large and probability is minimum where amplitude of the wave is small. « 2.8. WAVE (PHASE) VELOCITY AND GROUP VELOCITY Phase Velocity (W or: ,). The velocity of individual de-Broglie wave is called Phase velocity. It is more than velocity of light. Group Velocity (u or v,). The velocity of group of waves ie. wave-packet is called group velocity and its velocity is equal to the velocity of material Particle with which wave packet is associated. Group velocity is equal to velocity of the moving particle (ie. u = v) Let us consider that a “wave group” (i.e. wave packet) arises from the combination of two waves, with the same amplitude A, but differing in angular velocity by da and an amount dk in wave number 7 (2. So the two interferring waves may be represented as. Y1 = Acos (wt — kx) Y2 = Acos [(w + dw) 1 (k + dk) x] ; The resultant displacement y at any time t and at any position x is the sum of y, and y,; using identity rhe (a- os (@=B) cosa+cosB = 2cos: 2WATTERWAVES AND UNCERTAINTY PRINCIPLE a ‘and since cos ( — 9) = cos 6, we have (Qe + de - - pen ene 2Acol 222400 = Ob + 2] (deta) Now elnca ce nd os ie tas a compared to w and k respectively Qa +do) = 2w (2k + dk) ms 2k y= 2A cos (wt — kx) ox (22), 7 (4);] wl) Equation (1) represents a wave of angular velocity w and wave number k which has superimposed ‘ dk upon it a wave (the process called modulation) of angular frequency (¥ a) and wave number (¢ ). ‘The effect of this modulation is to produce successive “wave groups” as shown in fig. (2.3). The “phase velocity” or “wave velocity” W is given by w= n= 22 22 (2) a Fig. 2.3. Beat formation while the “group velocity’ u of the “group of waves” is given by dw do _ de . ue Ge 3) du ‘The angular velocity # and wave number k of the de-Broglie wave associated with the particle of rest mass ma and moving with velocity v are given by m2) 2am, @ = das 2a\"— T (4) 1-3) si-2)MODERN'S ATOMIG,AND MOLECULAR PHYSICS (B.Sc. I) And 28 an(@) » ay (5) 2 dk Now let us find the value of 5 and To pnd From Eq, (4) or (6) dk To find = From eq. (5), an x = tem 2)? A 2 1 3 dk _2nmy{,_ v2)? 2zmo% (-3) 2) *(-3) wk i +h 2 2 2 3 = 22m (2) 2{, 2 2 “a ( 3] [:-5+5 ay ck _2xnm 2 : -2m,-2] o. | MATTER WAVES AND UNCERTAINTY PRINCIPLE “a3 _ Group velocity = Vel f material particle “o p velocity = Velocity. of mi ; : . The de-Broglie “wave group” aseocited with a moving particle travels withthe same velocity as that of the particle. The “phase velocity” or “wave velocity” W of de-Broglie wave evidently has no simple physical significance in itself. - 2.9. RELATION BETWEEN PHASE- VELOCITY (v,) AND GROUP VELOCITY (v,) “The phase velocity of a wave having frequency («) and propagation constant k is given by | ) FZ pk or w= ku, we]) >= i cts is given by The group velocity of the wave having frequency —~ and propagation constant ~~ is Bh aes : ; 8 dk . Using Eq. (1), we get i €y,, yo 4 2 = Eltvy)= E+, v= dy or U, = UY tee wn(2) Also, k= 2k 3) 2 2 dk = ra Dividing Eq. (3) by (4), we get k a s-a ofS ak "aa = Putting Eq. (5) in (2), we get | Aw, 7 ; Mg = eae ‘xperiments of Davisson and Germer. First of all in 1927 the two American physicists, Davisson and Germer predicted experimentally the electron waves predicted by de-Broglie. Davisson and Germer were studying the reflection of electrons from nickel target which was subjected to such a heat treatment _ that the crystal was transformed into a group of crystals. In this case the reflection become anomalous and the reflected intensity showed striking maxima and minima. They then suspected that the beam of electrons might be diffracted from the crystals like X-rays. This shows that electrons behave like waves under certain circumstances. ‘The experimental arrangement is shown in figure 2.4. The electron beam is produced from what is known as electron gun. F is the filament which is heated to dull red. Electrons are emitted from the filament due to thermionic action. Gis system of electrodes with central holes maintained at increasing :“a MODERN'S ATOMIC AND MOLECULAR PHYSICS (B.Sc. I) Potentials. By this arrangement, clectrons emerges as a well collimated beam. These monoenergetic electrons fall on the target T, a single crystal of nickel. ‘Some of scattered electrons entered the Faraday cylinder C known as collector. The collector current was amplified and measured with a sensitive galvanometer G. The collector can be moved on a graduated circular scale S to receive electrons scattered in varicus directions. The collector has two walls insulated from each other. A retarding potential is applied between the inner and outer wall of the collector such that only fast moving electrons coming from electron gun may enter into the collector and Le Not the secondary slow electrons coming from |_| LAQY target. The slow electrons will be reflected from the X retarding potential. The whole apparatus was \N enclosed and highly evacuated. N ‘The experiment was conducted in two different © ways, ie., (@ for normal incidence. (ii) for oblique incidence. Fig. 24 ~ @ For normal incidence. In this case the beam of electrons falls normally on the surface of the crystal. The collector was moved on the circular scale to various positions and galvanometer current was recorded at each position. The galvanometer current is a measure of the intensity of diffracted beam. A graph was then plotted between the co-latitude (angle between the incident beam and the beam entering the collector) and galvanometer current. Several curves were obtained for different voltage electrons which are shown in figure 2.5. ULL Fig.2.5 It is observed that a bump begins to appear in the curve at 44-volt electrons. This bump moves upward as the voltage increases and attains the greatest development for 54 volts at a co-altitude of 50°. Above 54 volts the bump again diminishes. These peaks (or bumps) observed at 54 V are due to consecutive interference of electron waves after diffraction from the crystal. It is found that the maxima in the diffraction pattern occurs, when Bragg’s condition is satisfied. ie. 2d sind = nh; o(l) where d is the distance between atomic Planes, A is the wavelength of the electrons and n is the order of spectrum. From the fig. 2.4, we have 0+9+0 20, = 180° - p = 180° — 50° = 130° 8MATTER WAVES AND UNCERTAINTY PRINCIPLE 4s For n = 1, Eq. (1) becomes A = 2dsind For Ni crystal, d=0-91 A =0-91 x 10-10 m a A= 2x oat x 10710 x" sin 65° a = 165 Also, for 54 V, the de-Broglie wavelength of electron is given by (theoretically) 12:27 As aa" 167A (2.4) Thus, the two results are in close agreement with each other. So Davisson-Germer experiment provides direct verification of de-Broglie hypothesis of wave nature of moving particles. (i Oblique Incidence at crystal face. Crystal is oriented so that the angle of incidence was 10° and the position of collector was also chosen corresponding to angle of reflection of 10°. The de-Broglie wavelength of the electron was changed by altering the acceleration potential V. The electrons suffer reflection of Bragg’s type and law governing this type of diffraction is nl = 2d sin. Fig. 2.6 (a). The electrons suffer diffraction from the successive parallel planes of atoms in the crystal. Now, as before, 1 the current is measured as a function of square root of acceleration potential V. Since A « Ww the graph between current and V!? also describe the relation between current and t . See fig. 2.6 (b). GALV. CURRENT 5 10 15 20 25 Ww. Fig. 2.6, (a) Bragg's reflection Fig. 2.6.(6) Fig. 2.6. Oblique incidence. A 1 -Broglie relation, 4 = mals Now, from de-Broglie relation, Tenn * Wa and Bragg relation gives, n = 2 d sin @ = constant 1 or nen n « vila (1) That is order of spectrum is inversely proportional to V2, The curve shows distinct maxima at regular intervals of V"2, confirming de-Broglie theory. 2.11 THOMSON EXPERIMENTS G.P. Thomson performed experiments with electrons accelerated from-10,000 to 50,000 volts. In his pPetiments, Thomson observed diffraction patterns exactly analogoue to X-rays patterns, moreover he was able to determine the wavelengths associated with Electrons. Since diffraction patterns are onlyae MODERN'S ATOMIC AND MOLECULAR PHYSICS (B.Sc. “ = ible provided the waves are associated with a beset panicle hence experiments supported the : concept of matter waves. His experimental arrangement is shown in Fig. 2.7. ‘The high energy electron beam is produced by the cathode C. The beam is excited with potential upto 50,000 volts. A fine pencil of this beam is obtained by passing it through the slit or diaphragm S. The accelerated fine beam of electrons now falls ona thin film F (of the order of 10° cm) of gold or aluminium. The photograph of the beam from the foil is recorded on a photographic plate P. Whole of |. the apparatus is exausted to a high vacuum so that '— the electrons may not lose their energy in collisions Fig.2.7 with the molecules of the gas. w ; After developing the plate, a symmetrical pattern consisting of concentric rings about central spot is obtained. This pattern is similar to that produced by X-rays. 1o be sure that this pattern is due to the electrons and not due to X-rays generated by the electrons in there passage through the foil, the cathode ays in the discharge tube are deflected by magnetic field. It was observed that the beam shifts correspondingly showing thereby that the pattern is produced by electrons and not by X-rays (X-rays Patter is not affected by electric and magnetic fields). The observed rings can only be interpreted by _ considering that the diffraction pattern of the incoming beam is due to the diffraction of electrons by the foil. As the diffraction pattem can only be produced by waves and not by the particles, so Thomson concluded that electrons behave like waves. Thus, Thomson experiments clearly demonstrated the existence of matter waves. He also calculated the associated wavelength and observed that it depends only on the accelerating voltage and is independent of the material of target. The wavelenghs obtained by diffraction patterns agree with the wavelength obtained by de-Broglie relation. 2.12, NEUTRON DIFFRACTION In 1936, W.M. Elsasser suggested that moving neutrons should have de-Broglie waves associated with them and that they could, therefore, be diffracted inthe same way as do the electrons. The relationship between wavelength 4 and momentum p of the neutron is still given by h_ih Asses, Pom,v = where m, is the mass of the neutrons. We know that the mass of the neutron is about 2000 times as large as that of an electron and hence the wavelength associated with neutron is about 1/2000 that of an electron of the same velocity. The relationship between energy E and wavelength A is expressed as h 1 _ 0-28 Yim E or A= TE’ (2) where d is expressed in A and E in eV. When E = 0-1 eV, A= 1 A which is required for diffraction work. It is also possible to confirm their wave properties for very much smaller wavelengths. For example, neutrons with energies of about 10 MeV are rather readily produced in nuclear reactions. Such neutrons have wavelengths of about 10-'? cm, The distance is comparable with the diameters of ‘most nuclei. Thus when fast neutrons are scattered by nuclei, the result is the characteristic diffraction pattern. The wavelength distribution can be measured by introduc'ng a crystal and a neutron detector as shown in Fig. 2.8. This arrangement is just like one X-ray diffraction apparatus except that a different detector used. The crystal and detector are turned in such a way so that the two angles shown as @ in the figure are equal. Reflection fiom the crystal occurs only when A and 0 satisfy the Bragg relation. The aMATTER WAVES AND UNCERTAINTY PRINCIPLE fraction of neutrons reflected asa function of 8 gives an experimental determination of wavelength distribution of the incident neutrons, Neutron diffraction has roved a useful method {or studying the structure of crystals, especially organic costal containing hydrogen, Ths sue ie fact that the scattering of X-rays or electrons by hydrogen is very weak ‘as Compared to the scatteri by neavier atoms and so the presence of hydrogen atoms in a crystal cannot be detected. Neutrons, on the other hand, interact with nuclei through nuclear forces and are scattered by hydrogen atoms. Neutron diffraction is also frequently applied d to the study of ™magnetic properties of Solids and various other allied ‘phenomenon. Since Fig. 2.8 Example 1. What is de-Broglie waveleniih of an electron which has been accelerated from rest through a potential difference of 100 V. ‘ mn. We have the relation - “ wo KQXre ae 2B: = 66 W Tae’ vt In this case V = 100 volts. 4 = 227 5 — , in this case V = de =12274 Example 2. An electron microscope uses 1-25 Ke . electrons. Find its ultimately resolving power on the assumption that this is equal to the wavelength ofthe electron, given that e=16x10%C m = 90x 103! kg and h = 6:62 x 104 Js Solution. Since wave length of electron in a potential V is given by a 12-27 5 _ 12-27 ig Po A 2 PY 10, a Ap . we yer oF ere E = 12:5 KeV V = 1250V aa = 2 19-m = 227, = 03474 A So the resolving power of the microscope is 0-351 A. 3. Find the energy of the neutron in units of electron volt whose ‘de-Broglie wavelength is 1A, Given mass of neutron m_= 1-674 x 107 kg. Planck's constant, h = 660x 10 Js Solution. We have the relation . h h ass mv mE aNMODERN’S ATOMIC AND MOLECULAR PHYSICS (B.Sc. Il) a ro or 2ma In this cse, m = 1674x107 kg A =1A=10m h = 660 x 104 Js 660 x 1074)? E ( y © 1.674 x10” x (10-9)? 13-01 x 10-217 _ 13-01 x10 1-6 x10-9 mute the de-Broglie wavelength of 10'! KeV neutron. Mass of neutron may be taken as a hers x Soe ke Solution. In this ios kinetic energy of neutron 10"! KeV = 10!4 eV = 10!4 x 16 x 10719 J = 8:12 x 107eV. 16x 10°55 1 Now gn = 16x 105 1 2x1-6x10-5 2 | or v= || ms 1-675 x 10 1 1-675x10-77 2 2x 1-6 X107> _ A _ 6-625x10-* mv 1-675 x 10-77 = 286 x 10-5 m. Example 5. What would be the wavelength of quantum of radiant energy emitted, if an electron transmitted into radiation and converted into one quantum, Solution. According to Planck, the energy E associated with one quantum E = hv, where v is the frequency of radiation. ‘When the energy of an electron is transmitted into radiation, we have the relation E = mc? (mass energy relation) he hy = me? or = Again =me2 _ hk 6-6x10-* me ~ 9-1x 107! x 3x 10° 0.0244 x 10-10 m = 0-0244 A. Example 6. Calculate the energy in electron volt of an electron wave of 4 = 3 x 10 m. Given h = 662 x 10-4 Js. Solution. We know that energy is given by the relation In this case, h = 662 x 10-4 Js, m= 91 x 107! kg and A =3 x 10 mMATTER WAVES AND UNCERTAINTY PRINCIPLE “9 (6-62 x 10-4)? Es 2x 9-1x 1079! x (3.x 10-2) 5 = 027x103) 0-27 x 10733 * 16x 10°? Example 7. Estimate the amount of accelerating voltage of which electrons are to be subjected in onder to associate them with de-Brogle wavelength of 050 A. Given that e = 16x109C eV = 1468 x 10-5 ey m = 90x 1075! kg | h = 662 x 10°94 Js Solution. Now if V is the accelerating potential measured in volts, then an electron will gain the energy E given by EseV h And A= — mv ae—t * Teme) h (meV) Therefore, substituting the values, we get 662 x 10-* 05x 103 = ———_ * [2meV) or Az (662 x10-™)? x 150 © (05x 1079)? x 9-0 x 1072! x 1-6 x 10-9 V = 614-4 volts, Example 8. Energy ofa particle at absolute temperature T is of the order KT. Calculate the wavelength of thermal neutrons at 27°C. Given mass of the neutron = 1-67 x 10” kg, Planck's constant, h = 6-60 x 10 Joule-sec. and Boltzmann's constant, k = 8:6 x 10-5 eV °C~!. Solution. We know that avers - = ine f2mE From the problem, E=iT h A= emkT) Here hh = 660 x 10-4, m= 1-67 x 10-27 kg T = 27°C = 300K k = 86x 105 eV 86 x 10-5 x 1-6 x 10719 Joc"! = 1:376 x 10° pctMODERN'S ATOMIC AND MOLECULAR PHYSICS (B.Sc. Il) 6-60 x 10-* 5 Yea x 1-67 x10-7 x 1-376 x 10"? x 300) = 1777x101 m=1-777A 9. Calculate the de-Broglie wavelength for an electron which has been accelerated through .d. of 28:8 V, given that onde 7 +6 x 109 C 1x 10°51 kg = 662 x 10° Js Ro Solution. — We have relation As = 208A Example 10. Calculate the velocity and de-Broglie wavelength of a proton of energy 10° electron volts, given that Mass of proton Charge on the electron Planck's constant = 6:62 x 107 Js, Solution. The energy of proton imi = 105eV = 105x 16x 10-19 (y leV 516 x 10-19) 2 _ 2x10°x1-6x 10" ye oaorerae ™m 2x 105 x1-6 x 107!" 16x 10-7 o 210° 1-6 x 107! a 1-66 x 10-27 = 4:39 x 106 ms“! The de-Broglie wavelength A is given by h A Az—e mu V@mB) According to problem, E = 10° x 1-6 x 10-19 6-62 x 10-4 des Yox 1-66 x 10727 x 105 x 1-6x 1079) = 93x10-4mMATTER WAVES AND UNCERTAINTY PRINCIPLE 51 Example 11. Calculate the de-Broglie wavelength of an a-particle accelerated through 200 volts, given that: m = 6576 x 1077 kg h = 6:62 x 104 Js Solution. We have the definition of potential difference between two points is defined as the work done in moving a unit positive charge from one point to the other. In this way the work done in moving, an a-particle between the two points between which the potential difference is V volts is given by E = 2eV Liga? 2ev l4emV h 4 Tlemv 6-62 x 107% 4x1 _ 662% 10-4 9-175 x 107% = 7215x103 m Example 12. What is the energy of gamma ray photon having a wavelength of 1 A. Given that : he = 662 x 104 Js Solution. We know that aa opete 6-62 x 10-4 Panam? 10? Energy of gamma ray photon E =pxe, where ¢ = velocity of light a y~34 Bx SB XIO™ 5. aot 107 2 x 1074 x 3 x 108 1° xiexi0® = 124« 104eV. Example 13. Calculate the de-Broglie wavelength of a neutron of mass.1-676 x 10-7 kg and speed 3003 ms-!, THPU 1999 (S)] m = 1-676 x 107 kg v = 3003 ms! de-Broglie wavelength, ho eee 6-62x 10-4 ooorss s = “mv = 1676 «10-77 x 3003 ~ "001375 x 10" 315 x 10-10 m 315 A| MODERN'S ATOMIC AND MOLECULAR PHYSICS (8.86) | 5 it je to potential differenc Example 14. Calculate the wave length associated with an electron subjected pone age os | 1-25 kV. Solution. V = 1-25 kV = 1250 V . Wave length associated with electron, 12-275 _ 12-27 5 ew” 56 = = =0347A Example 15. Determine the de-Broglie wavelength of an electron, having kinetic energy of 1 eV Given mp of an electron = 9:11 x 10! kg and h = 6:625 x 10 Js. a Solution. Here the kinetic energy of the electron is very small as compared with its rest mass energy, i.e. 0:512 MeV and hence negligible “ m= m= 911 x 10! kg 1 KE. of the electron (m=) = leV = 16x 10795 2x 1-6 x 107! vs m : h de-Broglie wavelength, A = aol Putting the values, we have 6-625 x 10-4 Vm m2x 1-6x 1079 6-625 x 10-4 32x 107! xm 6-625 x 10-4 - vax 1079 x 9-11x 1073! = 123x109m = 1234 JAa3, HEISENBERG’S UNCERTAINTY PRINCIPLE / After the discovery of wave nature of matter, it was very difficult to define the word ‘particle’. Classically, the position and momentum of a particle can be determined simultaneously and precisely at every instant of time. However an interesting consequence of matter wave is that we cannot simultaneously specify the exact position and momentum (ie. velocity) of any particle because a group of wave is always associated with a moving Particle (called wave packet) as shown in fig. 2.9. All that we can say is that the particle is some where within the wave packet and a certain inaccuracy always crep in defining the position of a moving | «—————_— ax particle like electron, proton etc. Similarly, we can Fig.2e say that there is a certain amount of inaccuracy in a ——->MATTER WAVES (AND UNCERTAINTY PRINCIPLE 53 determining the velocity and hence the momentum of the particle. Heisenberg uncertainty principle state that the exact position and momentum of a particle (say electron or proton etc.) cannot be determined simultaneously with a desired accuracy. “fax is the uncertainty in the position x ofthe particle and Ap is the uncertainty inthe corresponding momentum p, then Ax. Ep = h [whére p= #1 ' sn(25) ~Proof. Heisenberg principle of a moving particle can be proved with help of de-Broglie’s concept of wave group. Let a wave group be ‘obtained from the combination of two waves having same amplitude A and 2x differing in angular velocities Aw and an amount Ak is wave number (4) and represented by the equations Acos (wt- kx) Yo = Acos [(w + Aw)t's (k + Ak) x] ‘The resultant displacement y at any time ¢ is given by yenty= oe hbeon + aye e+ ADs (2w + Aw)t—(2k + Ak)x Aw Ak Cd or y = 2Acos [: cosa +cos B = 2 cos Beas =F] ‘Since Aw and Ak are very small as compared to w and k respectively. (2m + Aw) = 2m and (2k + Ak) = 2k So Eq. (1) becomes ‘Aw _ Ak y =2A cos (wt — kx) oor ~4h,| (2) Equation (2) represents a wave of angular velocity w and wave number k which has superimposed Ak upon it a wave of angular frequency *e and wave number —. Due to modulation ‘a wave group" is : bo formed having wave velocity Ug = 7, ‘Thus the position of the particle in the wave group can not be given by certainty, it will lie some where between two consecutive nodes Fig. 2.10. Fig. 2.10 ‘The condition for the formation of a node is given by cos A -4,) 0 .MODERN'S ATOMIC AND MOLECULAR PHYSICS (B.Sc. i) or Aot-Akx = (2n+1)0 ~ F be the position of two consecutive nodes, then abled Bot Ak, = (2n+ I and ho.t- Ake, = (2n+3)n Subtracting Eq. (3) from (4), we get Ak (x -%)) = 2 2a or nome So uncertainty in the measurement of position of the particle (x, — x2) Oe (5) asa . 2x Since = : ase Sap So Eq. (5) becomes or Ax. Ap =h, where Ap is the uncertainty in measurement of momentum p. or Ax. Ap2 ph Another from of uncertainty principle (Time-energy uncertainty relation) Time energy uncertainty principle state that the exact time and energy of a particle can not be deterimined simultaneously with a desired accuracy. If AE is the uncertainty in the measurement of energy E and Ar the Corresponding uncertainty in the ‘Measurement of time 1, then AE. At> Proof. ‘The kinetic energy of a particle of mass m moving with velocity v is given by Bw coeel If the mass of the particle is constant then the uncertainty in the measurement of E is given by AE = ($m?) 1 nvAv=v (mAv) or AE = vAp Since ve = Ax AE = ApQUANTUM MECHANICS 3.1, NEWTONIAN MECHANICS AND QUANTUM MECHANICS, The fundamental difference between newtonian mechanics and quantum mechanics lies in what it is that they describe. Newtonian mechanics is concerned with the motion of a particle under the influence of applied forces, and it takes for granted that such quantities as the particle’s position, mass, velocity and acceleration can be measured. This assumption is, of course, completely valid in our everyday experience, and newtonian mechanics provides the ‘‘correct’’ explanation for the behaviour of moving bodies in the sense that the values it predicts for observable magnitudes agree with the measured values of those magnitudes. Quantum mechanics, too, consists of relationships between observable magnitudes, but the uncertainty principle radically alters the definition of ‘‘observable magnitude’’ in the atome realm. According to the uncertainty principle, the position and momentum of a particle cannot be accurately measured at the same time, while in newtonian mechanics, both are assumed to have definite, ascertainable values at every instant. The quantities whose relationships quantum mechanics explores are probabilities. Instead of asserting, for example, that the radius of the eleétron’s orbit in a ground-state hydrogen atom is always exactly 5:3 x 10-!! m, quantum mechanics states that this is the most probable radius ; if we conduct a suitable experiment, most trials will field a different value, either larger or smaller, but the value most likely to be found will be 5:3 x 10-1! m. At first glance, Quantum mechanics seems a poor substitute for newtonian mechanics, but closer inspection reveals a striking fact : Newtonian mechanics is nothing but an approximate version of Quantum mechanics. The certainties proclaimed by newtonian mechanics are illusory, and their agreement with experiment is a consequence of the fact that macroscopic bodies consist of so many individual atoms that departures from average behaviour are unnoticeable. Instead of two sets of physical principles, one for the macroscopic universe and one for the microscopic universe, there is only a single set, and quantum mechanics represents out best effort to data in formulating it. 3,2 Oasx we 3.10. HAMILTONIAN OPERATOR The total energy operator E is usually written in the form H=->-—t+V 3.9) and is called Hamiltonian operator.MODERN'S ATOMIG AND MOLECULAR PHYSICS (8.86, ) 78 i be written as + ‘Since time independent Schrodinger equation can ee ue (ES =Eyp i or Hy =By : 3.11. OBSERVABLE IN QUANTUM MECHANICS AND ITS SIGNIFICANCE Observable . Ke sasurement with a physical system is A quantity which is obtained by the process of observation us eet of an observable in a system ig termed as observable in quantum mechanicsxThe result of measurement Of a coach expressed by a number and observable is always a real entity as it is revit & “obetnrable the cae peat, However, since the act of measurement disturbs pliysical system, the ee Sad oe depends on the interaction between the system and measuring device and is thus spread over some mean value. The value of observable generally depends on time and so time is a universal parameter and not itself an observable. If the observable does not vary wit - Physical constants like rest mass and electronic charge or charge on a proton etc. belong to this class of observable. 1. : . The basic drawback of classical mechanics is that, in it, it is assumed that : _f!) measuring process does not disturb the system. . . Alll observables are the characteristics of the system irrespective of the measuring device. id most ofthe observable of the system can be measured with great accuracy. ; lowever in quantum mechanics the above short comings are overcome because it explains : i) An observable, though characteristic of the system, depends on the measuring device. (i) Simultaneous measurement of conjugate variables like position and momentum, time and energy requires = application of the Heisenberg’ s uncertainty principle to account for the error in measurement of the observable. (iit) Observable like position co-ordinate, linear momentum components, energy of the system have the same meaning as in classical mechanics but observable like spin, symmetry, parity etc. have no equivalence in classical mechanics. 2. EXPECTATION VALUE | ~~ ‘The probability of finding a particle at a particular point in Space is given by the absolute square of the wave function, : PG.) = vey =l oP any experiment measure some dynamical quantity which is defined by space is momenta and large number of trials of observing that quantity are made tei ‘elative, sper of times the particle is detected in a volume element in a particular state give the probability. The average value or expected value of any function f(F) under this definition can be expressed as <1@)> = SFP sfordr= f y+ Gye vein PO, 1 de = F(x, ) (x, 1) de Let us discuss following cases (D Expectation value of position (x) Since probability of finding a particle inthe interval x and x + dx The observed value of at wh aie petite lue of x at whicl i is i value of x in time ris associated by wave farses eee re raed and she mean of the observed of x-coordinate of the particle at time t ie. if a particle is found m wives, called expectation value of snore oti 1» times in region x, and mp times in Expectation value of x is given by ith time, it is constant of the system, °QUANTUM MECHANICS = Sue a = Dan a” oo Daa tm ton i n where p; = 7 is the probability of occurance of value x, where p; is the probability of occurance of a value x;. If the variable x is continous instead of discrete, the sum is changed to integral. = fxPndr = fytanvnde Thus we use the average number of measurements of x to characterize the position of particle at time 1. This average value of x-coordinate at time, is called its expectation value. (ii) Expectation value of position vector (7) ‘The interpretation of the wave function in terms of the position probability density makes it possible to calculate the average or expected value of the position of the particle. We write the expectation value of 7 as } SrereovG.ndr “ 2 (1) S v@ove.n dr For normalized wave function p “ S vrGFovGndr 21 So Eq. (becomes = f ernry@ndr (2) Since positron vector, 7= xit+yj+zk , So we get three equations = f p*@nxpndr = f v*o.nyvOnndy <> = f ptanzpland: Similarly the expectation value of potential energy V is given = fv Gov eGndr~ MODERN'S ATOMIC AND MOLECULAR PHYSICS (B.Sc. It (ii) Expectation value of momentum ‘The expectation value of momentum is given by 2 - .

= fv Hd pylatdr +3) To solve the above integral, we have to find the value of p.on function of X but uncertainty principle does not allow to find the value of p and x simultaneously,'$0 we try another method. ‘The wave function y for a particle having linear momentum p and energy E is given by yoo) = Ae CEP) av _ i a imeem ax = APAC or pye — ; Putting Eq. (4) in (3), we get

= fy «xo(~in Z}pcnae cs

= -ih fv wn Zvcande (iv) Expectation value of energy The expectation value of energy E is given by = f¥@DE Vand ao ‘The wave function of a particle havi : ; is given by ' particle having energy E and linear momentum p moving along + X-direction VD = Ae UME px) = - Ey ume __E m 2-7" or Ep = or 7 Putting Eq. (6) in (5), we get ihe 5 * (6) t a = fy wo(in2) pana ied inf ¥ wo vende 6 :QUANTUM MECHANICS, 81 3.13. DEGENERACY If there is more than one lineraly independent wave function belonging to the same energy eigen value E, the energy level is said to be degenerate. If there are r linearly independent wave function (y,, Poo Pn) belonging to the same energy state, then the energy level is said to be fold degenerate. It can be easily shown that any linear combination of the degenerate wave functions of the form, . = CWP) + C2 + + Vy is also an eigen function belonging to the same energy eigen value.We will prove this for n = 2 the generalization is straight forward. Since , and 2 are eigen functions belonging to same eigen value E,, we have the relation 2 ey In ge TVG = Ev @ and wd vy tn at +V@)¥2 = Ey, (2) ‘Multiplying the equation (1) by c, and the equation (2) by cy and adding, we get wd “Trae om F cph2) + V@) (q+ C22) = E, (cp + er2) +-(3) which shows that the linear combination cy), + cs is also an eigen function belonging to the same eigen value E,. So the case can be extended to any number of states. EXACT STATEMENT AND PROOF OF UNCERTAINTY / PRINCIPLE FOR WAVE PACKETS Precise definition of uncertainty . Before making an exact statement of uncertainty principle let us give a precise definition of uncertainty. The uncertainty in measurement of an observable fis defined as Of = [-7}!%, (3.11) where. = fv Pur on(3.12) Thus uncertainty in the measurement of an observable is the square root of difference between the mean of the square and the square of the mean of fin the state w. Exact statement of uncertainty principle Uncertainty principle state that the exact position and momentum of a particle cannot be determined simultaneously with aesired accuracy. If Ax is the uncertainty in the measurement of position x of the particle and Ap is the uncertainty in the corresponding momentum p, then h Ax. Ap = > eo) Let — Ax and Ap be uncertainties in the measurement of position and momentum of a particle. We define these uncertainties in x and p by the relations Ax = [e2>-< ol? : (2) and Ap = [-

?j!2 (3) Consider two arbitrary well behaved functions f and g of space coordinates. Let us define three integrals. a=ffifdr b=ffigdr c=Sa'gdr 4)MODERN’S ATOMIC AND MOLECULAPPHYSICS (B.Sc. Il) So SlrtePar = far re raftarar = fa rrersas oe +f spars See “Pr where 2 is a parameter which is assumed to take real values. Using Eq. (4); we get SlytePar = 2 atie' tbr (5) Since the integral on the L.H.S. of Eq, (5) is positive, so 22a+A(p" +b)+c = O forall values of A. ‘Thus for the above inequality to be satisfied, we must have dac = (b" +b)? or ac 2 fo+8 *? (6) Putting Eq. (4) in Eq. (7), we get . SP erfeedr = Lfre+ war] ) Let us consider the special cate of =Oand

=0, and Ietus assume the following functions : f= mpo-int and g sixy. * SP serfeaer = sl wt) oP esemvrurver fs * . = 0 SZ Rar fy ey dr - 7 av" ay ® SfaraS F Marc?> (<2 >= Sv'2y @r) Sof f'rarf ged = 8 Sfoaly 1 -sy Btalee> But ve = Oatx=t 0 Srrerfeeer = 1hv(- or SPIO Seeds = p> <2> (8) : ie ? ol [s . a ae 7 oy” . And SU e+ fear = Ja wovscmBcwyle,s a ‘ or SUf'et fo) er= +) SExvarans #.v"| ‘92d ay" . . =A seers fy y Pr fy vars f Rave] ay" . , . A avers sy yartf 2% 2,)- Fy vel -h [2 wp Pr-f vy # Since p is normalized, so y*x y would vanish at x= + ©. Suter feyar = -nfo-fy'yar]anfyyer or Set fear = +h [fv vd'r=i] Putting Eq. (8) and (9) in eq. (7), we get m 2 pr 2 5 or [xp?>]!2[cx?o]!2 z or Ap.Ax 2 2 This is Heisenberg’s uncertainty relation. 3.15. ORTHOGONALITY OF ENERGY EIGEN FUNCTIONS ‘Any two normalized wave functions YY, 2) and Y_ (x ¥, 2) corresponding to two different eigen values E,, and E, of energies are said to be orthogonal, ifthe integral of the product of one of them and the complex conjugate of the other over the common domain of the functions is zero. ie. S Ym¥ndt = JS Vivnde =0, if man wal) Since the wave function are normalized, it mean that +e inn aT Lif m=n (2) where dr = dx dy dz is the volume element Proof for One Dimensional Case Let pq (x) and y, (2) be any two normalized non-degenerate eigen function of the one-dimensional Schrodinfler time-independent equation for a Bound particle with corresponding eigen values E,, and E, of energy. ‘The one-dimensional Schrodinger equations for y,, and Py ite given as w dy, om ad VYm = En Ym (3) ® dy, mage +Vn = Eve (4)u MODERN'S. ATOMIC AND MOLECULAR PHYSICS: BS.) | ‘The Schrodinger equation for y?, which is the complex conjugate of is the Same as that for y,, so longs the pote energy ira; o we have \ Ete ew, = EnV ao Multiplying eq. (4) by y*, and eq. (5) by y,, we have vr 7 Py, *: — Fyn + Wn Ya = Evie J Fy Swi, = EihVe O Now subtracting eq. (6) from eq. (7), =| = Em ~ En) ¥nPn 2m . - or SA = En EnV . d(d ay, d (dyn), Wn dy «| sa} 4h {t}24 2m . =FEn~ En) Yin¥n h + d¥n)_d{ d¥mn) 2m . a (va) Sf, = FE, E,)Vaie d{. dv. dy 2m or oly, eras vita} | een En Vins inpuing bt tt nh ne bia to: +o d{ dv, dm os es on Yn Ge Yn aha. = SE,-E )f72 vin de + Wy ay," 2m oo or [vests Tee oe -te,- Ey) f 72 Vinvn ae 8). . dt For a good wave function, y and spproach Zero as x > + 0; so the left hand side of eq. (8) becomes zero at both end points. 2m +o 6 En ED) S72 Um Unde =0 (9)QUANTUM MECHANICS 8s Ne ee If the wave, function belong to two distinct energy levels to that E,, # E,, then we have 0 oe Pm Pade = 0 (form # n) +0(10) For m= n, the factor E,,- E, = 0. In this case according to the physical interpretation of wave function we must get +0 ow Ym Yndt = 1 (form=n) (1) So the wave function shows the orthogonality property. ‘When two or more linearly independent wave functions p,, 2, V3. -»- correspond to the same eigen value of energy, E, then the energy is said to be degenerate. Such wave functions are not necesarily orthogonal. But it is possible to find orthogonal linear combinations of degenerate wave functions in many different ways. For example, a linear combination of , and p is the wave function given by the relation , Pe = Cy + C2Y: y-can be made orthogonal to , by choosing the constant coefficients c, and cp such that Svivede = 0 or Sv avi tev)dr = 0 Sub vide-to, futvade = 0 4 Vivade ore ¢. = =e aa 2 J iba: oe Syivde ’s Equation for the Complex Conjugate Wave Function y* (x, y, 2, t) We have the time-dependent Schrodinger equation of the wave function p (x, y, z #) is given by wooo _ pd -E Vet wy = ae I) Since p is complex, s0 we may write Y =o tidy =+(2) where p and are real functions of x,y, 2,1. Putting this form for in eq. (1), we get 2 a a -— V2(yy + iva) + Vr + iV) = Ps + a) Equating real and imaginary pats on either side ofthis equation, we get the following two equation: 2 Avi +1 = nee anh 3 (3) 2 HL viy eve = AGL ld) Multiplying eq. (4) by — i and adding it to eq. (3), we obtain » wy, 2 ih 2[y, +22 ~ FV iv) + V 1 ~ ia) = br (» 7 a = -ih>- (v1 - ya) The complex conjugate p” of p is given by ve = ve 5) h . . oy So vv eve = -int 6) This is the equation for y* _—O_O _—— —_ OM SIMPLE SOLUTIONS OF “ SCHRODINGER EQUATION 4,1 PARTICLE IN A BOX asi infinite potential well) - inc pa ne inn eps a ie. the particle moves only along a straight line say along x-axis. Let the alla of sh Pox be rigid, elastic and non-penetrable. Let the particle can travel along x-axis between x = O and x = L. Let the collision of the particle with the walls be elastic so it does not loose energy. Let us represent this by an infinite square well potential as shown in Ppa TIEEE figure 4.1. H The potential V is defined as H . ) Va = 0 fordL H Classical view <«———— |______+} Classically, the particle can have any value of energy. If E=0, the particle will be at rest inside the box and if E > 0, the particle will move along x-axis and at x = 0 and x = L, it will experience a force = -& (Since V = 00, so F = e) in the direction opposite to its motion and is reflected from the walls and thus moves back and forth along x-axis. Quantum view i: ‘The Schrodinger wave ‘equation for the wave function of a particle moving along a straight line in the presence of external field is given by @y 2m wen), (6) 7) sone(8) ‘where n i called quantum number. Since E depends on n so let us denote the energy of the particle by Ey. Hence above equation gan, be written as age : nah E, = mi? ‘ 1 Thus E, « n?, ae E,* 7 Energy level diagram (or Eigen values of energy) Forn~ 1, the value of E,, will be minimum and is given by . er ee DL ‘This is called ground level energy and the state is called ground state. The energy corresponds to higher states is called excited energy and the states are called excited states. These are given by Paw Sar ne 32 2p2 Fe op 3 = me we(9) sxe 10)104 MODERN'S ATOMIC AND MOLECULAR PHYSICS (B.S. 1) 4 => =16, ea 1 and so on. : B,—-Heace icle can have any value of energy given by Ey, 4, 9E,, 16E},...He oop guniet Testioeas Values of energies ofthe patcle are called energy levels or eigen values of energy, shown in fig 4.2, and are not equally spaced. values of momentum ‘The linear momentum of any one of the allowed value E, is given by Ph = 2mE, Using Eq. (8), we get or Pn = = (n=0, 1,2 en) ‘Thus momentum is also quantized into discrete allowed values. Hence the momentum of a particle inside the box is (directly proportional to the quantum number n ie. Py & n 1 Gi) inversely proportional to the length L of the box ie. py & L (iii) independent of the mass of the Particle. energy Fe minimum possible energy possessed by the particle inside the box is called zero oint energy. ‘The energy of the particle inside will be minimum at n= 1 So zero point energy we 1 oar (see Bq. 9) Since E = Ois not allowed because if E=0, then y = O everywhere inside the box and th density in the box | /? = O ie. the particle isnot inthe box. hence E Hence, the panicle can not have zero total energy inside the bos, so ti cannot be at rest in the box (quantum mechanically). Wave function, From Eq, (6, the wave function y (x) of the particle inside the box is given by _ * yQ) =Csin ke wn(12) Using Eq. (7), We get : ien probability ¥@ =C sal + Probability y density ° P =¥"@) YQ) =¢ sa) cain or yey =C2sin2 a ——SIMPLE SOLUTIONS OF SCHRODINGER EQUATION 105 Since the probability density between x = 0 and x = L is 1, because the particle is somewhere within this boundary. ‘i s . * ) 2 Mn 2nn ie fy vas 21) w-|2 = L nx ; or oo fsin’ Fax 2 0 L or =1 or =l1 a, 2anx 529 or ail i foT =01 © 2 255 or e =T_ ae ant Le (13) ‘The normalized wave functions 1, and 5 together with the probability densities jy, ly2/* and vs? are plotted in fig. 4.3 (a & b). Although y, may be positive as well as negative but | Yq P is Fig.4.3 always positive and since ,, is normalized, its value at a given x is equal to the probability density of finding the particle there. In every case |, ? = 0 at x = 0 and x = L, the boundaries of the box.MODERN’S ATOMIC AND MOLECULAR PHYSICS (B. $0, 106. The probability of the particle being present may be very different for different quantum number, pek (maximum in the middle of the box) a ea é the middle of the box) =0 (in the middle o ; ; tee a pt! in staat energy level of n = 1 is most likely to be in middle of the bor, white 4 particle in the next higher state of n = 2 is never there. Classical physics, of course, suggests the same probabilit the particle being anywhere in the box. . . Enamel, A vrtclels moving inone ‘dimensional potential box (of infinite height) of width 25 A, Calculate the probability of finding the particle within an interval of SA at the centres of the box when itis in its state of least energy. Sane ; ; Sotution. We ow the the wave functions of a particle enclosed with an infinite potential well is given by 2 max v@) = yrsin ‘When the particle is in the least energy state n = 1, hence in this case 2 mx vi) = fanz At the centre of the box x = L/2, The probability of finding the particle in the unit interval at the centre of box is given by 2. a(L/2) 2 a 2 p- | |—sin2 int 2 iveore| ce | cin ser ‘The probability P in the interval Ax is given by P=|y@) Par = Zax In this case L = 25 A = 25 x 10-! m and Ax= 5 A=5 x 10-10 m x5x107!0 p22 x10 ~ 25x10~'9 Example 2.4 proton or a neutron in a nucleus can roughly be regarded as a particle in a the surface of the nucleus plays the role ofthe wall of the box and proton moves more or less freely fete these walls. What is the energy released when a. ‘Proton makes a transition from the first excited state to the ground state of a box of nuclear size i.e. 1-0 x 10-4 m ? Solution. We have r= 1 x 10-!4 m, and m= mp = 1-67 x 10-27 kg. ‘The energy of ground state is determined from relation n tp? ; 2myr?* ee ® x (105x107 Js)? 2 ~ = mgr” 2X167X10-" kg x (10x 107 4m)? =33x 10-13) Energy of first excited state will be 2 A? By = POG =4x33x 1035 - = 13-2x 10-3 J‘SIMPLE: ‘SOLUTIONS OF SCHRODINGER EQUATION By -E = 13-2 10-3 3_3.3y 10-35 713, =99x 1013s = 29x10"™ 16x10-3 = 6-2 Mev, Example 3. A particle is confined to a one-dimensional infinite ic ic is ; 0 potential well of width 0-2 nm. It is given that where the energy of the particle is 230 eV, its eigen function has 5 ntoaden Find the mass af the particle and show tha i can never have energy equal to 1 keV. Solution. Since the eigen function correspondi i Particle isi eee oe de eaen Rson cr ing to energy 230 eV has 5 antinodes, the particle is in Es = S?E, =25 B, =230eV so that E, = 92eV =92x16x 10-195 4-7 x 10-19 J Also, L=02nm=02x 109 m=2x 10m 2p 2 2 Now E, = i= pase 2 mi? ‘ . 6625x1074)? 8VE, 8x4x10- x147x10- = 93x 101 kg For E,=1keV,n should be such that ie, Since n is not an integer, E,, = 1 keV is not a permitted value of energy. Example. 4. Calculate the value of lowest energy of an electron moving in a one-demensional force Sree region of length 4 A. . (HLP.U. 1997) Solution. We have m = 9-1 x 10-7! kg, L=4 x 107! m Since energy of electron in nth state is given by 222 nh 2mi? 8m? Po (6625x107)? Bm? 8x91x10 x (4x10? Ey =0376x 10-8J or Example. 5. Calculate the value of momentum and energy of an electron in a box of wavelength 1A, forn=2. [H.P.U. 2000 (S)] Solution. We have L =A = 1A = 10"! m,n=2 , nth _ nh Since thomentum, Py = “3- = 3p Forn = 2 2% 6625x10-** = 1 Py =~ aggro KBE Py = 6625 10 kg ms“!MODERN'S ATOMIC AND MOLECULAR PHYSICS (8.5, Pty? 2p? n And energy, Om? = aad Forn=2 _ 4% (6625x1074)? 2 © 8x91x10-! x10" Ey = 1508 eV. Example. 6. A particle of mass 10 kg is moving with a speed of 104 m s! in a box of length 103 4, Assuming this to be one dimensional square well problem, calculate the value of x /) Solution. We have m = 10 kg, v = 104 ms“!, L = 103 A= 10-7 m Since energy of a particle in nth state is given by nah? B= 2 _2mUE, — 8ml7E, n= he or n= 2mLv _ 2x10~6x1077 x107+ or ne zx 106, h 662510" Example. 7. Evaluate the expectation value for kinetic energy of a particle in one dimensional rigid box in the nth quantum state. (H.P.U. 1998) Solution. We know that the wave function of a particle enclosed in one dimensional box is given by 2. (nax € vi « Ful The expectation value of kinetic energy E is given by oo o 2 P = * = * —wdx = f p*Epdx f vw 1 i = Sy Lot in? yd ra ay spy kY, am SY at Ej fale Balt =” fan( 2 we in ae Sol ae i L‘SIMPLE SOLUTIONS OF SCHRODINGER EQUATION 109 2 92p2 L, wa o = =) Sin? = ae (-ve sign is omitted) Oo L ft ~cos288 ac a = rer mi 2m? 4.2. POTENTIAL STEP (Energy less than step height) Potential barrier : If the force field acting on a particle is zero or nearly zero everywhere except in a limited region, it is said to be a potential barrier. A single step potential barrier is shown in fig. 4.4. At x =0, the force field acting on the particle is Vo, where Vo is called the height of the potential barrier. The step potential can be represented as (0 for x <0 (region I) VO@)= |v for x>0 fy for x >0 (region I) In region x < 0, the particle moves like a free particle and as it approaches the step potential in region x > O, it faces the potential height V (x) = Vo as shown in fig 4.4 ee INCIDENT WAVE) Classically a particle in region I can move freely as the force field is zero but at x = 0, discontinuity occurs. Since energy of the particle is less than the height of the potential barrier i.e. E < Vo and the VO=0 | EeVy particle is in region I, so it will remain in region I for ever. If sometimes the particle is moving towards the positive x-direction, it will be completely reflected back at x = 0. Fgaa Quantum mechanical view Since the potential Vo does not depend on time, so we apply time independent Schrodinger equation to solve this problem. — ‘Schrodinger’ one dimensional (along x-axis) time independent wave equation is-given by zy 2 Z + FFE-Vy=0 seu 1) InregionI. V =0 So Eq (1) becomes ay | 2mE ae da orf athe =0 e2)MODERN'S ATOMIC AND MOLECULAR PHYSICS (B.Sc. I) 110 where k= PE wo 2 In region II V = Vo So Eq. (1) becomes dy , 2m(E-Vo) fy. =0 ae ”Y ; # co ke we iy | or be 14 = (4) where ky aul) ‘The general solutions of Eq. (2) and (5) may be written as ° w-e(6) v= Adht + Behe Lo vu = Ceh* + De®” where A, B, C and D are arbitrary constants and are to be evaluated. In region i.e. x >0, the term De'?* increases rapidly as x increases ie. ¢4* ->© for x > 2 making yy ©, which violates the boundary conditions (i.e. yj has to be finite everywhere) hence the term De'?* is rejected. . Ym = cena . wD) ‘The values of A, B and C can be determined by using boundary conditions. Boundary conditions In the given situation, the boundary conditions are that the eigen function and its first derivative should be finite, single valued and continuous, hence (Ow must be finite and continuous at x = 0 ie. [vi].-0 =[¥u],—0 From Eqs. (6) and (7), we have A+B =C ~@) di oy = must be finite and continuous at x = 0 : av) favo ne [e)..-[1., From Eqs. (6) & (7), we get ik, A-ik,B=-kC or ik (A-B) =-kC or ik, (A-B) =?kCSIMPLE SOLUTIONS OF SCHRODINGER Equation 7 14 or A-Bs Be (9) Adding and subtracting Eq, (8) and Eq, (9), we get = fy 4 te z A= (+2) t- (10) = C{,_;% wa and Bs 5 inet w(11) Putting the values of A and B in Eq, (6), we get Cf ke) yx . C(, ike = [14s |eitix 4 Lf _ the) ine WI 3! Bet Si Ps je (12) Also from Eq. (7), we have Vu = Ce“hx (13) The first term of Eq. (12) represents the incident wave and second term represents the reflected wave . = £4 Hee) ike = fy He) aye and Pre = s( iE Je Reflection coefficient (R) jthe reflectance ot reflectivity or reflection coefficient at the potential discontinuity may be defined as follows. The reflection coefficient (i.e. the fraction of incident particle reflected) is equal to the ratio of reflected probability density current 10 the incident probability density current. Reflected probability density current Incident probability density current Density current of a free particle is the product of velocity ~ vy and probability density yy) Cf, _ the) itis Cf the ) ity ( a2), S{i+H}e Re Re Weve 2 UVind or R=1 Thus we find that the incident wave is totally reflected and this is same as predicted by classical consideration. In region II (x > 0) the transmission coefficient vanishes but the wave function is not zero. It means that there is a finite probability of finding the particle in classically forbidden region x > 0. The shape of Wave function in the two regions is shown in fig. 4.5.we MODERN'S ATOMIC AND MOLECULAR PHYSICS (B.Sc. I Peay 1 In order to observe the particle inthe region x > O, it must be localized within a distance Ax = b ‘and its momentum must be uncertain by Ape pb = Im {Vo -E 4.3. POTENTIAL STEP (Energy more than the step height) A single step potential barrier. is shown in 46. fig “le i "At x =0, the force field acting on the particle is Vo, where Vo is called height ofthe potential barrier. ‘The step potential can be represented as (0 for x<0 (region) VG) = |v for x>0 (region) Classical View Classically a particle in region I can move freely as the force field is zero but at x = 0, it experiences a retarding force, F = = towards the left and its velocity decreases and it would not be reflected at x=0 because the particle has enough energy to enter the region x > 0, thus classically, the particle is always transmitted. Fig. 46 Quantum mechanical view Since the potential Vo does not depend on time so we use time independent Schrodinger equation to find the motion of the particle in regiogs I and I. Schrodinger time independent one dimensional wave equation (along x-axis) is given by ay 2m wie =0 nfl) In region I v=0 So Eq. (1) becomes @y | 2mE ate =o @ Si Satie =0, a mE yy where ee 3) Inregion IT V = Vo So Eq. (1) becomes 2, ~ LY , 2ME-Vy) 7 ae w 0) the term De~2* is rejected because there is nothing in region Il to cause a relection of wave, and hence in region x > 0, there is only a transmitted wave. o vun= Cet wT) The value of A, B and C can be determined by using boundary conditions. Boundary conditions In the given situation, the boundary conditions are that the eigen function and its first derivative should be finite, single valued and continuous. (i w must be finite and continuous at x = 0 ie. [vileo = [¥uh-0 From Eq (6) & (7), we have A+B =C (8) a (ii) 2 must be finite and continuous at x = 0 ie (= AL. From Eqs. (6) and (7), we have ik,A ~ iky B= ik,C La AoE wn) or ky (9) ‘Adding and subtracting Eqs. (8) and (9), we get c(,,% sf +h) i (10) k and B= Simi) L— (LL) ky Putting the values of A and B in Eq. (6), we get Cf, ko) piyx 4 Cf) 2) ite w= Sli t2)e +5lI-Fle 02) Also from Eq. (7), we have vu = CelMODERN'S ATOMIC AND MOLECULAR PHYSICS (B.Sc. I) 4 ‘The first term in Eq. (12) represents the incident wave, second term represents the reflected wave and Eq. (13) describe the transmitted wave. Cf, , ke) it ie. Vin = Sst. ie = £{;-22) nme el st i}. ‘ Vir = Celt ivi i ie it transmissivity or ‘The reflectance or reflectivity or reflection coefficient and the transmittance or transmission coefficient at the potential discontinuity may be defined as follows : Reflection coefficient (R) a. i aa The reflection coefficient is equal to the ratio of reflected probability density current to the incident probability density current. s{i-Blm Sli lee And R= Weve 2h 4 2\ kh : Minin Lf ke) ita Cf be) mite hy 27%, If 2 2 4 1-2 2 . & (: =e) Re = 4 (14) “ ph] “(nee & ‘ From Eq. (14), we find that R < 1, but > 0, And R > O if ky = ky and R > 1 as ky > 0. [2m(E=Vo) [2mE Butky = cen ted by 2 pat Sok, = kif Vo=0 and hence the reflection willbe zero only if Vg is equal to zero, Therefore, there must be some reflection even when E> Vo, This is in contrast to classical mechanics where R = 0 for E3 Vo, ‘Transmission coefficient (T) Zhe transmission coefficient is equal to the Fatio of transmitted probability density current to the incident probability density current. fe Te ei Py mC cet ie k Unit mt "st+B)eS[+B le = Pu ae “ PL (ky +h) Since Pi= VImE = kh coewen Pu = J2m(E=V) = kyh [Using Eo (5) 2 Ts fh sat ~ Shik fe Kh (ky +hy) (+h) a /.gmPLE SOLUTIONS OF SCHRODINGER EQUATION ee From Eq. (15), we find that T < 1. This is in contrast to classical mechanics where T = 1 for E>Vo- ‘Thus we find that the behaviour of quantum particle is quite different from that of a classical particle. ‘According to definition the sum of reflection coefficient and transmission coefficient must be unity. Thus rete ch) mh) shaky (4th) the? = (4th «1 2 (ki +h) Example 8. Show that the reflection coefficient for a step potential with E > Vo can be written as v2 1-1-2 (-2) 1/2 14{1-%2) E NV and find its approximate form when i <1. Solution. The reflection coefficient for such a step potential is given by fy _ [am(E-Vo) k= w 2mE Ng For %o << 1, using Binomial theorem and neglecting the terms containing higher powers of == we get6 MODERN'S ATOMIC AND MOLECULAR PHYSICS (B.Sc, i) ‘OTENTIAL BARRIER OF FINITE WIDTH AND HEIGHT (Tunnel Effect) we consider a paricle incident on a barrier of the type shown in fig. having width ‘a’ a with the condition that the energy of particte E < Vo and the barrier potential is given by 0 for x<0 (region!) V(x) =4Vo for 0Q, (region III) + Vo) ! Ve=Vy INCIDENT WAVE REFLECTED WAVE E ky *) 2 14+) sinh*(ka) lz ky ; 2 b_k } sinh? <7 (ka) ly he a Eq, (23) measure the probability that the particle is reflected from the barrier. ‘Transmission coefficient (T) The transmission coefficient is equal to the ratio of transmitted probability density current to the incident probability density curent. f R= R= (23) cosh? (kya) + ( Transmitted probability density current ae T= “Ticident probability density current Veer or T= Suter VVin Pint Feltiagt ihe or te ae [ou=]120 MODERN'S ATOMIC AND MOLECULAR PHYSICS (9, » Peel or Ts AA Using Eq, (18), we get Te—_ FF Ike YL FF’ | cosh? (kya) +—| =2—4L] |einh’ (kya) 4k ky cosh? = 1+ sinh?) 2 1+sinh?(k,a)] 1+ Baap ky 1 on T= 2 2, Race heal a | Dik, sinh?(kya) Putting the value of ky and ky from Eq. (3) and (5), we get 1+ 1 ————. (24) ‘Thus T # 0, hence we can say that the particle has certain Probability of penetrating the barrier and Teach the region III, which is contradictory to the classical prediction. ‘The transmission is based on ‘tunnel effect which may be stated as under : 'fa particle is impinging on a barrier with energy less than the height of the potential barrier, it will {ot necessarily be totally reflected by the barrier but there is always probability that it may cross the barrier and continue its forward motion. (Fig. 4.8). The tunnel effect can be understood in terms of the uncertainty principle; if we say that the incident particle cannot enter the barrier, then the uncertainty Ax in its Position must be 0 there. But since Ax Ap > 4/2, the corresponding uncertainty Ap in the particle's momentum must be infinite inside the barrier. An infinite uncertainity in p means that p, and E as well, must be infinite, which is not compatible with the finite momentum and energy of the particle. Therefore, the particle must be able to enter the barrier, and once inside it has the possibility of continuing on, ‘The tunnel effect actually occurs, notably inthe case of alpha particles emited by certain radioactive nuclei. An alpha particle whose kinetic energy is only a few MeV is able ne escape from a nucleus Fig. 4.8SIMPLE SOLUTIONS OF SCHRODINGER EQUATION 121 whose potential wall is perhaps 25-MeV high. The probability of escape is so small that the alpha particle might have to strike the wall 10°8 or more times before it emerges, but sooner or later it does get out. Tunneling also occurs in the operation of certain semiconductor diodes in which electrons pass through the potential barriers even though their kinetic ‘energies are smaller than the barrier heights. 4,S:HARMONIC OSCILLATOR ~~ A parti le undergoing si iple harmonic motion is called a harmonic oscillator. In a harmonic oscillator. the force applied is directly proportional to the displacement and is always directed towards the mean position. If applied force displaces the particle through x, then Restoring force F is given by Fa ed or F=~kx _ (kis force constant) en) The potential energy of the oscillator is = —f Fax or Va kf ade = (2) (3) @ = \[-~ is called angular frequency. The classical frequency of thé oscillator v is given by wo 1 fk 2x 2aVn on) There are various ways to write the solution to Eq. (3). A common one is x= A cos (wi +) = A cos (27v1 +) where v is the frequency, A is the amplitude and @ is the phase angle which depends upon what x is g ENERGY a altime t= 0 2 Ifa graph is platted between V(x) and x, the graph will be a parabola as shown in fig. 4.9. ITE is the total energy and A is the amplitude of the motion, we find that at points x = + A, where YE are called turning points Fig.4.9.gMPLE SOLUTIONS OF SCHRODINGER EQUATION 15 v. Penetration distance of the particle inside the step 1 h h Axe set ky © f2m(Vy-E) © 2n,/2m(Vo —E) : 6625x1074 2x3442x V2%4x 107! x2.x 1075 = 22x 10-2 m Example 10. Find the barrier penetration factor for electrons of kinetic energy 10eV through a barrier 2A thick and width Vp = 20 eV. Solution, Here E = 10eV = 10 x 1-6 x 10-95 = 1-6 x 10-18 J a= 2A =2x 10 mVo= 20 eV =3:2 x 108 m= 91 x 103! kg Barrier penetration factor 1 ve ‘2m(Vo - E) 1+ ‘i inh? 0 N25 ef Ve _ G2x107!8)? a 4E(Vg—E) © 4x16x10-'® x16x107 Y= sinh |2"¥o—E) e ee Tz 2 Since = ———} = 0006208 1+(126516) Example 11. What is the condition under which a particle travels through the barrier without any reflection ? Solution. The barrier penetration factor (ie. transmission coefficient) for a particle having kinetic energy E through a barrier of thickness ‘a’ and with V9 is given by Nb +— 0 _ 4E(Vo - E) For perfect transmission, T = 1 1 —=1 2 = 1418 inn? [2m = BD, 4E(Vq - B) W 2 2m(Vo — 8) i or Vi ginn? |MM0- Bg EM -E) W fam(Vo - E) or sinh? pre, =0y MODERN'S ATOMIC AND MOLECULAR PHYSicg 22 126 2m(Vo —E) or : or or = nl2 : Hence the barrier thickness should be integral multiple of half the de-Broglie wavelength for Petey transmission of the particle. seeps eee OBJECTIVE TYPE QUESTIONS 5 1, The energy of a particle in one-dimensional box of width L varies as @L OL v= (©) Lt (@ L 2. Particle in a box is (a) one dimensional barrier problem. (6) Two dimensional barrier problem. 5 (c) three dimensional barrier problem * 3. The energy of a particle in ‘one dimensional box of width L (a) increases with width () decreases with width (©) independent of width 4. The energy of a particle in one-dimensional infinite well is (@) Ean (DE « n2 1 OE« + Obes 5. The reflection coefficient for a Particle on a potential step with energy less than step height is @1 Oo 1 . 1 > 6 @ 5. 6 The transmission coefficient T for a Particle on a potential step with energy more than step height. @T= “ @T<1 (T=0 @T=0 7. The zero point energy of a harmonit¢ oscillator is (@) zero ©) hw 1 3 () zhe (d) zhw 8. The energy of one dimensional harmonic oscillator in first excited state is @o (0) Srey 3 hy 5 > @ Sho a _—