EZ Ca ae ATOMIC SPECTRA AND MODELS INADEQUACY OF CLASSICAL PHYSICS Sir Isaac Newton made the first attempt to study nature of light. He proposed corpuscular theory of light. According to this theory light consists of tiny, perfectly elastic, invisible particles called corpuscles. These particles travel in all the directions in straight lines with velocity of light. According to this theory velocity of light is more in a denser medium than in a rarer medium. This theory could not explain the phenomena of interference, diffraction and polarization. Huygen’s developed wave theory of light. According to this theory, light travels in the form of waves in a hypothetical elastic medium called ether and he considered light as propagation of mechanical energy. Huygen, Young and Fresnel were able to explain phenomena such as interference, diffraction and velocity of light in different media. Then Maxwell proposed electromagnetic theory of light. According to this theory light consists of electromagnetic waves with electric and magnetic fields are associated in planes perpendicular to the direction of Propagation of waves. Although electromagnetic waves theory of light could explain most of the Phenomena but it fails to explain the phenomena like photoelectric effect, Compton's effect and emisson of light etc. Although classical theory was able to explain almost all the observable Phenomena upto the end of nineteenth century. But it fails to explain the later discoveries like X- ays, radioactivity, distribution of thermal radiations from a black body, low temperature specific heat of solids, photoelectric effect, electronic structure and optical spectra. In addition to these phenomena, lot of experimental observations of black body radiations 4nd optical spectra could not be explained by classical theory. (i) BLACK Bopy RADIATION CURVES The energy density E(v) of black body radiation only depends upon the frequency (v) and "perature of black body. The experimental curve of (spectral) energy density E(v) versus v at a Particular temperature T of black body radiation is shown in Fig, 1.1. '(2) ATOMIC SPECTRA AND MODELS Weins try to explain the spectral density E(v) [7 x ay versus frequency (v) curves on arguments based on thermodynamics. His expression was found to be in agreement with experimental results only in the high frequency region. Similarly Rayleigh and Jeans attempted to explain these curves by assuming these | E(v) black body radiations as electromagnetic radiations They estimated the number of modes of vibrations per unit volume in the frequency range v and v + dv and derived the expression for spectral energy density E(v). But their expression agreed with v > experimental curve only at low frequencies. Thus methods based on classical theory fail to give a single Fig. 1-1 formula that could agree with the experimental curve of black body radiation for entire frequency range. (ii) OPTICAL SPECTRA Different chemical elements show character’ Balmer derived an emperical relation for wavelength i. istic emission spectra consisting of discrete lines. the spectral series of hydrogen atom for the 1 a > =R-- > ole 2 & 2) a where R is the Rydberg constant and n = 3, 4, 5. atom and derived the formula for the wave number of from the outer orbit n, to on inner orbit n,. Later on Bohr gave theory of hydrogen emitted light, when an electron jumps of hydrogen are : (a) Lyman Series When m= 1 and n2=2, 3,4 This series lies in ultraviolet region. (b) Balmer Series When n= 2, and nz = 8, 4, 5... This series lies in the visible region of spectrum, (c) Paschen Series When ni = 3 and nz = 4,5, 6... This spectral series lies in infra red region.ATOMIC SPECTRA AND MODELS (d) Brackett Series When mi = 4 and n: This spectral series li 5, 6, 7. in infra red region (e) Pfund Series When ni = 5 and n2=6, 7, 8. This spectral series lies in infra red region, The classical theory failed to give the correct interpretation of these spectral series of hydrogen atom, (iii) PHOTOELECTRIC EFFECT When light of suitable frequency is incident on a metal surface then electrons are emitted from it. This phenomena is called photoelectric effect. The emitted electrons are called photoelectrons. Various experimental observations led to various conclusions, known as laws of photoelectric emission. 1, The emission of photoelectrons takes place only when the frequency of incident radiation is above certain critical value of that metal. This critical value is called threshold frequency. The emission of photoelectrons starts as soon as the light falls on metal surface ie. the photoelectric emission is instantaneous. 3. The maximum kinetic energy with which the photoelectrons are emitted from a metal surface is independent of the intensity of the light and only depends upon the frequency. For a given frequency, the number of photoelectrons emitted is directly proportional to the intensity of incident light. The energy distribution of the photoelectrons is independent of the intensity of the incident light. Although attempts are made to explain these aspects on the basis of classical theory, but different conclusions remained unexplained. (iv) SPECIFIC HEAT OF SOLIDS Solids are generally characterized by the regularity of distribution of atoms. The atoms are bound together by means of chemical bonds. Consider 1gm of a metal has N atoms or molecules (where N is Avogadro's number) which are coupled by elastic forces, They cannot change their Positions and hence cannot have translatory and rotatory motion. They can only vibrate about ‘ir mean positions. The atom vibrating along a line (say x-axis) has only kinetic and potential “nergy. Therefore atom has two degrees of freedom. Since atom can also vibrate about y-axis and “axis, therefore, in all atom has six degrees of freedom. According to the law of equipartition of “nergy, the energy associated with each degree of freedom is Sar where k is Boltzmann's constant and T’ absolute temperature. Hence average energy per atom = 6x5 AT = 3kT.ATOMIC SPECTRA AND MODELS Therefore total vibrational energy per gram of a solid containing N atoms E=3NkT | or E=3RT where R = Nk called gas constant Thus for a solid, the specific heat per gram atom which is known as Dulong and Petit's law. The graph Cvversus T for solids is shown in Fig. (1.2) At ordinary temperatures, solids generally obey this relation, which is based on classical theory. However, when temperature decreases the specific heat also decreases and becomes zero when T= 0°k. ‘Thus classical theory failed to explain the variation of. specific heat of solids with temperature. BLACK BODY RADIATION Every body emits energy in the form of waves (ie. electromagnetic waves) due to it : temperature. These radiations are known as thermal radiation or heat radiation. Whenever a body emits thermal radiation, it loses heat energy. On the other hand, a body gains heat energy, whenever it absorbs thermal radiation Thermal radiation lie in the infra-red region of electromagnetic spectrum. A perfectly black body is one which absorbs heat radiation of all wavelengths incident on it. It neither reflects nor transmits any of the incident radiation and therefore, appears bl whatever be the colour of incident radiation. When a black body is heated, it emits radiati which are known as black body radiation. In actual practice, no natural object strictly posses: the properties of a perfectly black body. But the lamp-black and platinum black are g approximations of black body. They absorb about 99% of the incident radiation. The simp most commonly used black body was designed by Fery. Fery’s black body. It consists of a hollow double walled metallic sphere with a narrow opening O on one side and a conical projection P on the inner wall exactly opposite to O as shown in Fig. (1.3). The space between the walls is evacuated to prevent the heat loss due to conduction and convection. Inner surface of the sphere is coated with lamp black and outer surface is nickel plated. The radiations which enter the sphere through the hole ©, suffer multiple reflections and is finally absorbed. Similarly when the walls of a cavity are heated toATOMIC SPECTRA AND MODELS (a5) are identical to light radiation with a difference of their wavelength. The wavelength of visible light is smaller than that of thermal radiatic El ENERGY DISTRIBUTION IN THE SPECTRUM OF A BLACK BODY RADIATION AND DISTRIBUTION LAWS In 1899, Lummer and Pringsheim performed an experiment to study the energy distribution of black body radiation. The experimental arranged used by Lummer and Pringsheim is shown in Fig. (1.4). The radiation from the black body pass through slit S; and fall on concave mirror C). After reflection from Ci, the parallel beam of radiation falls on a fluorspar prism, which is transparent to heat radiation (infra-red). The radiation passing through prism suffer dispersion. The dispersed beam of radiation is brought to focus on a thermocouple or bolometer by means of another concave mirror C2. The bolometer or therm ple is used to measure the intensity of radiation in different regions of the black body radiation spectrum. The experiment was repeated for different temperatures of the black body. Then curves between intensity and wavelength for different temperatures are drawn as shown in Fig. (1.5). From the study of these graphs following conclusions are drawn : Fery’s black body Siefae Fig. 1.4 () The energy is not uniformly distributed in the radiation spectrum of a black body. For both long and short wavelengths, the energy emitted is very small. (ii) At a given temperature, the intensity of radiation increases with increase of wavelength and becomes maximum at a particular wavelength. By further increasing the wavelength, the intensity of heat radiation decreases. (ii) For a given temperature, there is a particular wavelength (A,,) for which intensity of radiation (E,) is maximum. ‘.a ATOMIC SPECTRA AND MODELS, (iv) The total energy emitted by a body at a particular temperature ig ¢, qual to the a under the curve corresponding to that temperature. o the area (v) An increase in temperature of the body causes increase in energy emission (i.e. high the temperature of body more is amount of energy is emitted). ee (vi) With an increase of temperature of the black body, the maxima of the curves shift towards shorter wavelengths. In other words, the value of (A,,) decreases with nee { of temperature. Fig. 1.5 DIFFERENT LAWS (I) WIEN’S DISPLACEMENT LAW While studying the distribution of energy in the spectrum of a black body radiation, th graph between intensity and wavelength (Fig. 1.5), it is clear that the wavelength correspon to maximum intensity of radiation (An) shifts towards the smaller wavelength with the inere of the temperature of the black body. Wien stated that the product of Am and ab temperature T of the body remains constant. ie. Am T = Constant or AmT = b where b is a Wein’s constant whose value is 2.898109 mK. (I) STEFAN’S LAW It states that, the amount of heat radiation (E) emitted per unit face area of a perfect black body is proportional to the fourth temperature T.eee oe ee [ATOMIC SPECTRA AND MODELS [17] ie, E«T E=oT v-s (L.5) or Where ois constant called Stefan’s constant. Its value is 5.67*10-° Wm 2K n’s law can be written as Ife is the emissivity of the body then Stef E=eoT™ 1.6) ‘The value of e varies from 0 to 1. Its value depends upon the nature of the surface radiating radiations. For perfectly black body, e = 1. Ifa black body A at temperature T is surrounded by another black body B at temperature To then Amount of heat lost by black body A= 6 T! Amount of heat absorbed by black body B = oTo# Hence, net amount of heat lost by body A per unit time per unit surface area. =oT!-oTy’ =o (T*—To!) Thus, E =o (T'-To') (1.7) (III) RAYLEIGH-JEAN’S LAW Rayleigh and Jean assumed that radiations in a cavity have degrees of freedom which correspond to the frequencies of the standing wave that are possible in the cavity and that energy is equally distributed among various degrees of freedom. ‘According to Rayleigh-Jean's law the energy density in the thermal spectrum in the wavelength range A and A + da is given by 8nkT EAdA = i dh wee (1.8) Where k is Boltzmann constant. Limitations of Rayleigh—Jean’s Law It is clear from above formula that the energy radiated in a given wavelength range dd increases rapidly as 2 decreases. For short wavelengths, E, increases and approaches infinity which is not possible. Thus the above formula holds good in the region of longer wavelength but not for shorter wavelength. (Iv) PLANCK’S LAW On the basis of quantum theory, Planck's d i u ry, Planck’s derived the following formul: distribution in thermal spectrum. Eee. B= Ste a. 9B (eheE ay w+ (1.9) Where h is Planck’s constant, ¢ the velocity of light and k being the Boltzmann constant. Re1. ATOMIC SPECTRA AND MoDELs ~ ER] pPiancr’s RADIATION LAW Tn 1900 Planck made an important hypothesis known as Planck’s hypothesis. He introduced a new concept of radiation known as quantum theory of radiation. It is based on the following assumptions. @) A black body radiation chamber is filled up not on harmonic oscillators (or resonate with radiation but also with simple of possible frequencies Gi) The oscillators can not emit or absorb energy continuously but discontinuously and descretely as an integral multiple of small unit of energy ie. energy of oscillator is quantised. This small unit of energy hv is called quanta or photon. In general, the possible values of energy for an oscillator of frequency vare € =nhv (1.10) where n is a positive integer ie. n , 2, 3... and h is Planck’s constant. IN be the total number of Planck's oscillator and E their total energy, then average energy 4 ‘of a Planck's oscillator is given by (1.11) According to Maxwell's law of molecular motion, if E is the energy, then number of molecules having energies 0, E, 2B, ... nE are in the ratio meeps PGIRT . BIRT ne! KI ete. If Nz is the number of resonators (oscillators) having energy zero, then number resonators Ni having energy E will be M= Neo kr Similarly number of resonators with energy 2E will be No = Ny c2lkT In general number of resonators with energy rE will be Nr = Noo/AP where k is Boltzmann's constant. Hence N=Not+ Nit N2+Ng+...+Nrt... or N= N,+Noe*? +o 257 4 Nie 82 *E + Noelle N=N. (is Shs tae ee tote reer) add N, | eat 2 or tah, atta (seat Total energy of these oscillators (or resonators) E=(OxN,)+EN, +2 Ng +8€ Ng +h Nr+.ATOMIC SPECTRA AND MODELS. [9] or HEN THIEN ewe is ene SMT 4 tpeNe eT s r Ultra violet light of certain frequency is allowed to fall on plate P. The collector C is made positive with respect to plate P by above 10 volts so that all the electrons ejected from P are immediately attracted by C. Keeping the | frequency of light and accelerating potential fixed, the intensity of incident light is varied and photoelectric current is noted each time. It is found that the photoelectric current is directly proportional to the intensity of incident monn light as shown in Fig. (1.7). Hence it shows that the number ssh. errr of photoelectrons ejected from photosensitive plate is OAT directly proportional to intensity of incident light. 2. Effect of Potential on Photoelectric Current Apply some positive potential to collector and allow light of fixed intensity I: and fixed frequency to fall on plate P. Increase the positive potential of C gradually and measure the photoelectric current each time. It is found that the photoelectric current increase with the increase of accelerating potential, till for a certain potential of C, the current becomes maximum beyond which it does not increase further for any increase in | Stopping accelerating potential. This maximum | Potential value of the current is called saturation current as shown in Fig. (1.8). Saturation current Current > Now decrease the potential given to the ‘omar e ea collector C to zero and then make it — potential increasing negative. As soon as C is given negative potential, the photoelectric Fig. 1.8 current decreases rapidly till for a sharply defined negative potential Vo of C, the current becomes zero. The retarding potential for which the photoelectric current just becomes zero is called cut off or stopping potential or stopping potential for this particular frequency of incident light. If the light of same frequency is used at higher intensity J: and above experiment is repeated, the saturation current is found to increase but the stopping potential remains the same. Thus the stopping potential is independent of the intensity of incident light provided its frequency remains the same. Since on applying small negative potential to C, the current does not immediately drop to zero, it shows that for light of given frequency, the photoelectrons are emitted with velocities ranging from zero to a certain maximum value. Electrons with greater velocities and kinetic energies are able to overcome the small retarding potential to reach C. When however, the(1.16) retarding potential becomes V. equal to stopping potential, the current drops to zero. It means the work done by retarding potential on the fastest electrons released must be equal to their kinetic energies. ATOMIC SPECTRA AND MODELS If m is mass of electron, ¢ its charge and v,,,, the maximum velocity with which it is released, then 1 , J mvdiax =eVo 1.31) 3. Effect of Frequency To study the relation between frequency of the incident light and stopping potential, the value of intensity of light at various frequencies is suitably adjusted so as to get the same saturation current each time when collector C is positive with respect to plate P. Now gradually decrease the potential of C to zero and then negative till the stopping potential is reached. The stopping potential is found to change linearly with frequency of light, being more negative for higher frequencies as shown in Fig. (1.13). It is clear from the various curves that if frequencies are in order v: > ve > ve then corresponding stopping 4 potentials Vi > Vo > Vs. It implies that an increase in frequency of incident light increases velocity and hence kinetic energy of the emitted electrons so that greater retarding potent required to stop them completely. On plotting stopping potentials (Vo) against frequency (W) incident radiation a straight line graph as shown in Fig. (1.10) was obtained. It is clear from the graph that for a given surface there is certain minimum frequency v, of incident radiation for which is stopping potential is zero. It is called threshold frequency for the given surface. Current > ‘Accelerating ——> potential ‘This means there can be no photoelectric emission from a surface, if the frequency of the incident radiation is less than the threshold frequency for the surface whatever may be the intensity of radiation. ‘Stopping potential (Vg) —> For a frequency even slightly higher than threshold frequency, there is almost instantaneous photoelectric emission from the surface of material even if the intensity of radiation is low. LAWS OF PHOTOELECTRIC EMISSION The above experimental observations ma; y be summarized fundamental laws of photoelectric emission. eaae [1.17] only when the frequency of incident lled threshold frequency, characteristic ATOMIC SPECTRA AND MODELS () The emission of photoelectrons takes place radiation is above a certain minimum value ca for that metal Gi) The emission of photoelectrons starts as soon as light falls on metal surface. In other words photoelectric emission is an instantaneous process: sng emitted is independent of the intensity of light and Gi) The velocity of the photoclect depends only on the frequency of the incident light Gv) For light of a given frequency, the photoelectric current is directly proportional to the intensity of light, provided the frequency is above the treshold frequency. [EU] EINSTEIN'S PHOTOELECTRIC EQUATION ‘According to Einstein when a photon falls on the metal, it interacts with the electron of the metal. During interaction, it transfer whole of its energy to the electron. If this energy is less than the energy required to eject an electron, no photoelectric emission can take place. If it is more than the energy required, then immediately the electron is emitted. According to electron theory of metals, the electrons in the emitter (metal) are retained in it by forces of attraction and the incident photons should be capable of imparting sufficient energy to overcome these forces of Sttraction before they can escape from the emitter as photoelectrons. As the incident photons penetrate several atomic diameters into the emitter, the photoelectrons originate at different depths in it. Those electrons which originate at different depths, lose a part of their energy in making their way upto the surface. Those electrons which are initially on the surface of the metal spend only a very small part of the incident energy for their libration and hence they come out with large velocities. Since no electron emission from the surface of metal takes place if the frequency is less than the threshold frequency (vo) for that metal. Hence the minimum energy of incident photon required, just for emission of an electron from surface of metal (i.e. with zero kinetic energy) is equal to hyo, this is called work function (Wo) of the metal. Woz five oo) When photons (radiation) are allowed to fall on the surface of a emitter (metal), photons strike the electrons of the metal and transfer whole of their energy to the electrons. The energy of photons is spent in two ways (@) A part of the energy of the photons is spent in librating the electrons from the surface of metal. This energy is equal to work function (Wo) of the metal. (b) Rest (remaining) of the energy of the photons is used in giving kinetic energy to the emitted photoelectrons. If mis the mass and v the velocity of a photoelectron, then its kinetic energy is given by KE. = 1 mv? 2 ‘Then using the law of conservation of energy Energy of photon = K.E, of photoelectron + work function of metal 5 pyeea melt (1.33)ATOMIC SPECTRA AND Mopeis Lis Where v is the frequency of incident photon. cere hy = > mv" +hvg eee, or mv” =hv- hvo 2 or dmv? = h(v-vo) (1.34) Equation (1.34) is known as Einstein's photoelectric equation. Explanation of laws of photoelectric effect from Einstein Equation ( The velocity (v) of photoelectrons only depends on frequency (v) of incident photon as m, h and vp are constant in eq. (1.34) Thus the velocity of photoelectrons ejected depends upon the frequency of incident radiations. This is first law of photoelectric emission. Gi) If the intensity of incident light is increased, the number of incident photons inereases, _ which results in the increase of the number of photoelectrons, because one photon emit one electron. This increases photoelectric current. Thus photoelectric increases with increase of intensity of incident radiations. This is second law of photoelectric emission. (a) If v < vp then kinetic energy of photoelectrons becomes negative, which is n possible. Hence no photoelectric emission is possible if the frequency of the inci photon is less than threshold frequency. This is third law of photoelectric emis (b) If the photon with energy hv > Wo, hits the electron, then the collision betw photon and electron inside the metal is considered as an elastic collision. collision between photon and electron and transfer of energy from p electron is a single event and hence emission of electron is instantan explains fourth law of photoelectric emission. PHOTOELECTRIC CELL (i) Vacuum type Photo Emissive Cell This type of cell consists of an evacuated glass tube. Inside the tube there are two el a semi cylindrical eathode or emitter of large surface area and coated with photo anode in the form of a wire (Nickel or Platinum) as shown in Fig. (1.11) Positive terminal of the battery and eathode is connected to negative of the provided with some insulating base through which pins are projected.,roMIC SPECTRA AND MODELS re tube are connected to these pins and the Mp the help of these pins photocell is wtp the socket and also connected to in femal circuit containing a micro ex mmeter and a load resistance R a When radiations of — frequen greater than the threshold frequency are incident on the ecathode, photoelectrons are emitted. These photoelectrons are attracted by the anode which is kept at high positive potential with respect to cathode. This results in flow of current in the circuit and microammeter shows deflection. Since the current is very small, it is amplified before using. If anode voltage is increased, photoelectric current increases until it attains the saturation value. Light Fig. 1.11 (ii) Gas filled type Photo Emissive Cell R To amplifier Photoelectric current in vacuum type photo emissive cells is small. In order to increase the current, tube of the photo cell is filled with some inert gas like He, Ne, Ar etc. at a pressure of 0.1 ‘o 1.0 mm of Hg. Now, when photoelectrons are produced, they strike the gas molecules, on their Way to anode and ionize them. This results in the increase in photoelectric current. However, in these cells variation of photoelectric current with intensity of incident radiation is not linear. ERY uses oF PHOTOCELLS Photocells are used in counting devices. Photocells are used to measure the temperature of stars. Photocells are used in television cameras for telecasting scenes. ‘These cells are used in automatic switching of street light. These are used to measure opacity of solids and liquids. In industry these cells are used to find the flaws (i.e. 10. These cells are used for finding the Planck’s constant. 11. These cells are used in burglar and fire alarms. These cells are used for reproduction of recorded sound in cinema films. holes) in metal sheets. ‘These cells are used in photometry to compare the illuminating power of two sources. These cells are used in photographic cameras for automatic adjustment of aperture.COMPTON EFFECT In 1921, A.H. Compton discovered that when a beam of monochromatic radiation (X-rays op y-rays etc) is allowed to fall on a substance, then this radiation is scattered. The scattereg radiation contain two components (i) one having a lower frequency or greater wavelength anq Gi) the other component having same frequency or wavelength. The radiation of unchanged frequency in scattered beam is known as unmodified radiation while the radiation of lower frequency or higher wavelength is called modified rad Compton effect. The Compton frequency and (iii) recoil elect ation. ‘This phenomenon is known as {tering results in giving (i) modified frequencies, (ii) unmodified ATOMIC SPECTRA AND Mopeis ‘ons. radiation. According to quantum theory of radiation, the radiation consists of energy packets called photons. The energy of each photon is hv where h is Planck’s constant and vis frequen of radiation. According to Compton the phenomena of scattering is due to elastic collision between two particles, the photon of the incident radiation and the electron of the scatterer. Compton gave an adequate explanation of this effect on the basis of quantum theory of ! When a photon of energy hv is incident on the electron of the scatterer at rest, it transfers some of its energy to the electron and lose energy. The scattered photon will therefore have a smaller energy hv’ than that of energy of incident photon (hv). Thus frequency (v) of the scattered photon will be less than the frequency (v) of incident photon. In other words wavelength (V) of scattered photon will be greater than the wavelength (A) of incident photon (ie. X > 2). The phenomenon of change in wavelength or frequency of the scattered radiation is called Compton effect. The change in wavelength (x’ — A) is called Compton shift, In the scattering process the electron gains kinetic energy and recoils with velocity (v). Theory of Compton effect Compton derived an expression for change in wavelength during scattering process considering following assumptions. yeaxis 4 Electron atnest Scattering Incident photon Energy (hv) momentum (*) Fig. 1.12ATOMIC SPECTRA AND MODELS i ( Electron is free and at rest before collision with incident high energy photon. (ii) Collision between incident photon and electron is elastic collision. Gi) After collision the relativistic mass of electron is considered. The assumption is justified for collision by high energy photons because only a small fraction of the photon energy imparts sufficient energy to the recoiled electron. Let us consider a photon of energy hy colliding elastically with an electron at rest. Even if the electron is bound to the nucleus, a small fraction of energy hy is used to free the electron (i.e. work function) is negligibly small as compared to the energy of photon and hence electron is treated as free. During the collision process, the photon imparts a fraction of its energy to the free electron, which in turn gains kinetic energy and recoils through an angle @ called recoil angle. After collision the photon is scattered through an angle @ called scattering angle as shown in Fig. 1.12 Before Collision Energy of incident photon = hy Momentum of incident photon = c Rest mass of electron (i.e. because electron is assumed to be rest) = mo Rest mass energy of electron = moc? Momentum of electron at rest = 0 After Collision Energy of scattered photon = hv’ hy’ Momentum of scattered photon = Mass of electron moving with velocity (v) = m +: Relativistic energy of electron = me? Momentum of recoil electron = mv Since the recoil electron moves at angle 6 after collision, resolve the momentum of electron in two rectangular components. Component of linear momentum of electron along X-axis (= mv cos 6) Component of linear momentum of electron along y-axis = mv sin 9 Since the scattered photon moves at angle @ after collision, resolve the momentum of Scattered photon into two rectangular components. Component of linear momentum of scattered photon along x-axis = cos © Component of linear momentum of scattered photon along y-axis = "™’ sing ¢[ATOMIC SPECTRA AND MODELS 1.22 n of energy, before and after collision, we have Apply law of ‘conservatio <3 Energy of system after collision Energy of system before collisio hy+mgc? = hv’+me" ++(1.35) Applying law of conservation momentum (i) Along X-axis Bio = 1 coudtmcoso or hy = hy'cos0+muecos or muccosd = hv-hv’cos0 ...(1.36) (i) Along Y-axis 0+0= & sin0—mvsind or 0 = hy’sind—muesing or mvesind = hv’sin® Squaring and adding eqs (1.36) and (1.37). we get m2v?c2 sin? 6+mv2c? cos” = (hv’sin6)” +(hv—hv’cos6)” my2c2 (sin? 6+cos? 6) = h2v’? sin? 0+h?v" + h2v” cos” 0-2h wv’ cos8 m®v2c2(1) = h2v’? (sin? 0+cos” @)+h2v" - 2h? wv’ cos® or mvPc? = h?v'2(1)+h?v? -2h? wv’ cos0 or mvc? = hv? +h?v — 2h? wv’ cos0 or mvc? = h?(v? + v’—2wv'cos0) From eq. (1.35) or oe me? = h(v=v)+mge2 Squaring both sides, we get mich = R(v-v)P +m ec! +2h(v—v/mgc2 24 = or mic = h? (v2 + _2wv)4m,2e4 42h (y= y Subtracting eq. (1.38) from eq. (1.40), we get mech — mye? mec? =h(v? + v2) 4m,2e4 +2h(v-v) 2 _ pe omer a8) pantie no ~2h* w’(1— co80)+2h (v—v’)mgc2 +mp2e4* 0ATOMIC SPECTRA AND MODELS or. or or or or or or or or ‘vv/(1—cos0) + 2h(v—v’)mgc” +myc* rc! = -2h? w'(1—cos0) + 2h(v— v’)mo 2h? w'(1-cos®) = 2h(v—v')m,c” ives Rar ay ame cos8) wwe eB ee ee ieee are rine (1-cos@) (1.41) £2 = * Geos) viv A (4 -cos®) «(1.42) mae ‘This expression for change in the wavelength (’—A) of the radiation is called Compton shift. The quantity —"— = Ag is called Compton wavelength. Moe From eq. (1.42), it is clear that Compton shift only depends on angle of scattering 0, as h, mo and c are constant quantities. It is independent of the nature of scatterer. Special cases (When 6 = 0°,cos@ = 1, then eq. (1.42) becomes us DS eae mee mee or V-A=0 Le. W=d It means no scattering and hence no change in wave length of radiation, which is the case of unmodified scattering.[ATOMIC SPECTRA AND MODELS 1.24 (ii) When 6 = 90°, cos @ = 0, then (1.42) becomes h 662x104 No2 = =m m 91x10" x3 x10" =0.0242A, This is called Compton wave length (0) Gii) When 0 = 180°,cos0 = 1, then eq. (1.42) becomes ie twice the Compton wave length (Ao). moe Hence as 0 varies from 0° to 180°, the wave length of scattered photon varies from 2 to jase mec » provided the incident photon is of very small wave length. Hence the Compton shift is maximum, if the incident photon is scattered in direction opposite to the direction of incidence. DIRECTION OF THE RECOIL ELECTRON (Relation between angle of recoil and angle of scattering) Dividing Eq. (1.37) by eq. (1.36) mucsind __ hy’sin0 muecosd —-hy—hv’cos0 or sin® hy’sin® cos cos0) ee tan 9 = —Vsino v=v'cos0 From eq. (1.41) or oree sees (35) ATOMIC SPECTRA AND MODELS Z : +(144) or wat av), 20 1+| 3 |28in" rey 2 Putting this value of v’ from eq. (1.44) in eq. (1.48), we get ae vsin@ : ae vfas{ 2s aint mc?) = sin® Z ) 14 2) arin con (ge 2 es sin® (Chives (1 cos) +| Tp] zsin? (ge = sin® 4 sind _ dain? +L asin mye 2 pene 2)" mac cos’. = 2 ( sing i | 20 mee’ cot tang = 7 i oe This is the required relationship between angle of recoil and angle of scattering.26 KINETIC ENERGY OF RECOIL ELECTRON The kinetic energy of recoil electron is equal to the the Compton's effect. ATOMIC SPECTRA AND MODELs decrease in energy of incident photon, in Let energy of incident photon = hy Where h is Planck's constant and v frequency of incident photon Energy of scattered photon = hy’ Where vy > v’ ~: Decrease in the energy of incident photon =hv~hy’ = Rest mass energy of electron = my +: Rest mass energy of electron = mac? Similarly energy of the recoil electron = me? +; Kinetic energy of recoil electron = me? — mao? = (m — m.)e2 Since kinetic energy of recoil electron is equal to decrease in the energy of incident photon, +: Kinetic energy of recoil dectron = h(v-v’) E= From eq. (1.42), Compton shift h moc AM = (1-cos0) Putting this value in eq, (1.46), we get vx (1 cos6) A me h 24+—(1- e080) ‘moc=z \ (27) ATOMIC SPECTRA AND MODELS *y HN - e080) or At i (1=cos0) or or — (A =clv) (1.47) hy 1+——5(1-cos6) moc” Put ny a positive quantity. hya(1 -cos®) CB 1+ a(1-cos6) ens This eq. (1.48) shows that K-E. of recoil electron depends upon scattering angle 6. Special cases () When 0 = 0°, cos 0 = 1, then eq. (1.48) becomes E=0 i.e. the electron will not recoil if scattering angle is zero. (ii) When 0 = 90°, cos 0 = 0, then eq. (1.48) becomes (ii) When @ = 180°, cos 6 = -1, then eq. (1.48) becomes 2hvo. 1420, ‘Thus maximum energy is transferred to electron E na + — | incident Scatlorer direction | Fig. 1.13 ys photons are scattered from carbon block in different directions and their intensities and wave-lengths are measured by Brage’s spectrometer. Ina typical experiment, the spectra of K, line of molybdenum after scattering by a carbon block at different angles were obtained, Compton found that for each value of 0, there are distinct intensity peaks for two wave lengths, one of which is the same as that of incident radiation 4 and other has a higher wave length 2 Intensity ——> > Wave length ——> —0-0 = 00° Intensity —_» Intensity —> Wiave length —> | Fig. 1.14 ) ‘The peak at 2’ is called modified peak. The measi = 45°, 90°, 135° etc. However at 0 = 0° of scattered X-rays with wave length at The following observations were ma wurements were made at : ka line. The variation various angles of scattering is shown it le from the experimental study,[4.29] ATOMIC SPECTRA AND MODELS [2.29] line having same wavelength as that of (i) At angle of scattering 0 = 0°, there is or incident photon. Gi) At each scattering angle 0 = 45°, 90°, 135°, there are two peaks, one line has a wavelength as that of incident radiation called unmodified line and second line has slightly longer wavelength ¥/ called modified line and magnitude of A’ increases as 0 is increased (ii) The change in wavelength is independent of the wavelength of incident X-rays and hence nature of scatterer (ix) ‘The change in wavelength was found to increase rapidly when scattering angle is increased. DUAL NATURE OF RADIATION Radiation has a dual nature. It means radiation sometimes behaves as a wave and sometimes as a particle. However this dual nature of radiation was not readily accepted because wave and particle nature of radiation have contradictory aspects. A particle is specified by its mass, velocity, momentum and energy. A wave is specified by its frequency, wavelength, phase velocity, amplitude and intensity. All of these are not independent of each other. A wave spreads out and occupies large region in space where as a particle occupies a definite position in space. Thus it is difficult to accept opposite ideas that light (radiation) is a wave which spreads in space and also a particle which is realized at a point in space. However this acceptance of dual nature is essential as explained below. @ Radiations including visible light, infra-red, ultraviolet, X-rays ete behaves as waves and successfully explained the phenomena of interference and diffraction. These phenomena require the presence of two waves at the same position at the same time obviously it is difficult for the two particles to occupy the same position at the same time. Thus we conclude that radiation behaves like wave. () Planck's quantum theory has successfully explained photoelectric effect, compton effect and black body radiation. He established that the radiant energy during its interaction with matter behaves as it consists of corpuscles (or particles). These 0 corpuscles are called quanta or photons. Thus radiation behave like particle Radiation, thus sometimes behaves as a wave and soi me other time as a particle i. it ha: wave particle duality. : = ESQ atomic spectra A line spectrum is observed called atomic spectrum. Fine s portance of line spectra. when the excited substance is in atomic state. Hence it is also spectral lines corresponds to definite energies, hence it is the30 ATOMIC SPECTRA AND MODELS Similarly second third and fourth excited states of mercury corresponds to energies 6.67 eV, 8.84 eV and 10.4 eV respectively. If energy more than 10.4 eV is given to mercury atoms, they get ionised. In returning back to ground (normal) state from second, third and fourth excited states, they mercury atoms emit photons of energies 6.67 eV, 8.84 eV and 10.4 eV respectively. The energies of the excited states (i.e. 4.86 eV, 6.67 eV, 8.84 eV and 10.4 eV) for mercury atoms can be plotted in the form an energy level diagram. In general, let energy of ground (normal) state is E) (say). Let E,, E,, Ey» are the energies of first, second, third ..... excited states respectively. For the sake of calculation, let us consider the ground level energy Hy as zero. Otherwise electrons have some energy in ground state. | = 3% ; Li | ae i / | it | | ae | = | area EQ EQ aes TTT) The energies Ey, Fy, E,, E;, mercury, the excited states energies 4.86 eV, 6.67 eV, 8.87 ¢ frequencies which lie in the violet and ultra violet regions. because of transitions from higher to lower excited state (i.e. V and 10.4 eV corresponds to The visible mercury spectrum is Ee to Ey, E, to H, ete.) In Fig. (1.15), arrows from lower to hii energy absorbed is equal to difference of ener; ~ E)), (Ez ~ E,), (B; - E,) and (Es phenomena. igher states represents absorption of energy. ‘gies between two states. i.e, , - E,), Ey — ~ B,) ete. The absorption of energy is also quantised lark lines, at the time of emission and absorption. During both emission an id absorption spectra, if ¢] a transition between two ener; ; ace By states (i.e. EF.) is d then E Ey = hyATOMIC SPECTRA AND MODELS ay] where E and E, are the energies of excited and normal (ground) states Aires he ---(1.50) or (E = Ep) where cis velocity of light in free space ED LINE SPECTRA (SPECTRAL SERIES) OF HYDROGEN ATOM When the electron in a hydrogen atom jumps from higher energy level to the lower energy level, the difference of energies of the two energy levels is emitted as a radiation of particular wavelength. It is called a spectral line. The wavelength of the spectral line depends upon the energy associated with two energy levels, between which transition of the electron takes place. For transition of electron between two energy levels, the spectral lines of different wavelengths are obtained. The spectral lines are found to fall into number of spectral series as shown in Fig. 1.16. The various series of hydrogen spectrum can be explained from equation using Bohr’s theory of hydrogen atom. vee (1.51) x where R is Rydberg constant. ny = inner oribit Fig. 1.16 n, = outer orbit 2 = wavelength V =wave number (1) Lyman Series : In this series the spectral lines correspond to the transition of electron from some higher energy state to the lower energy state corresponding to n= 1. Therefore, for Lyman series, n= 1 and n,= 2,3, 4, so... arte: eqn. (1.51), the wavelengths of the spectral lines constituting the Lyman series are an by where ni =2,3,4 0.0. ‘These spectral Lines lie in ultra-violet region. f (2) pele Series : It is from some higher energy state to the lower energy state corresponding to n= 2 the series in which the spectral lines correspond to the transition of‘The wavelengths of the spectral lines y= 2 and n, = 3; 4, 5; Therefore, for Balmer seri in Balmer series are given by --(1.53) where ‘The spectral lines of this series lie in the visible region. : It is the spectral series in which spectral lines correspond to transition 3. (3) Paschen Serie: 8 of electron from some higher energy state to the lower energy state corresponding to n,= ATOMIC SPECTRA AND MODELS Thus for Paschen series, n/= 3 and n;= 4,5, 6 .... The wavelengths of the spectral lines in Paschen series is given by figs (el os ieee a lz Bl where n; =4,5,6. The spectral lines of this series lie in infra-red region. (4) Brackett Series : It is the spectral series in which the spectral lines correspond to transition of electron from some higher state to the lower energy state corresponding to nj= 4. Here, n,= 4 and n=5, 6, 7, .... The wavelengths of the spectral lines in this series are given where =5, 6,7, ... ‘The spectral lines of this series lie in the infra-red region. (5) Pfund Series : It is the spectral series in which spectral lines transition of electron from higher energy states to the orbit having n,= 5. Here n/=5 and n,=6, 7, 8...... The wavelengths of spectral lines in this series are where 1, =6,7,8. This series lie in the infra-red region, RITZ RYDBERG COMBINATION PRIN N DIAGRAM OF ALKALI ATOMS) oo Atoms of alkali metals (je. lithium, electron in their outermost orbit. The hydi sodium, potassium, rogen atom also hz3) i ; i. ATOMIC SPECTRA AND MODELS [2.33] point of view, the type of spectra obtained in e: electron are known as alkali spectra, Therefore these spectra can be represented by relation of the type used to represent hydrogen spectrum. Singly ionised atom of beryllium, magnesium, calcium and doubly ionised atoms of boron and aluminium have only one electron in their outermost orbits, therefore they give rise to alkali spectra es where the outermost orbit has only one rum is represented by a relation of the type +157) where R is Rydberg constant, v is wave number and Ais the wavelength. In this case 1 ig P fixed having p= 1, 2, 8..... and +. is the running term having q 2 p but always a whole number. q In case of elements giving alkali spectra, the atoms are not so simple as that of hydrogen hence there is modification in their fixed and running terms. Therefore the relation for alkali spectra is written as ies 1 i 1 eae ee | ae ie aes +.-(1.58) a es a where a and Pare characteristic constants for the elements whose spectrum is to be investigated. The investigation of alkali spectra shows following spectral series. (1) Principal Series : For this series p = 1 and q >2. Let characteristic constant for this series is f,. then this series is given by relation = t. oh =R Goleman ++-(1.59) a ae @-B" | (2) Sharp Series : For this series p = 2 and q 22. Let B, be the characteristic constant for this series, then this series is given by the relation > A ile is = so «+.(1.60) 2 Neos ae roy (8) Diffuse Series : For this series p = 2 but q > 3. Let iu be the characteristic constant for this series, then the wave numbers of the components of this series are given by - i T 2 eee ore s [ess a (4) Fundamental or Bergmann Series : For this series p=3 and q 24. If characteristic “onstant for this series is f}, then wave numbers of this series are given by 1.61) wy =k 1.62) pe Te seh e (@-)? (@-B,)ATOMIC SPECTRA AND MODELS [1:34] Let us take an example of lithium spectral series taking p = 2, a= q=3,4,5..... respectively. Then this series is written as 0.040 and B= 0.405 and disshe_by: i (1.63) vy = R|— ——— Z (2-0.040)? (q - 0.405)” In order to write down other series with the help of above series, we make use of Ritz Rydberg combination principle. According to this principle, the running term of the given series can be used as the fixed term of the series in question. Hence we can write the another series of lithium with the help of relation (1.63) by taking its running term as a fixed term for the new series. Therefore, we write the new series as 1 (1.64) (q - 0.040)" | where q= Similarly the another series may be written as v=R tent Uiirime= Sve Hee (8- 0.405)? (q- aaa where q=4,5,6... SCATTERING OF ALPHA PARTICLES Fundamental discoveries concerning knowledge of atomic structure have developed Rutherford investigation of scattering of a-particles by matter. An o-particle is a positiv charged particle having mass equal to four times the mass of hydrogen atom and positive cl equal to twice the charge of a proton. They are found to be emitted by many radioactive substances and usually carry high energy. If a sharply defined pencil of o-rays is made to fall or a photographic plate in vacuum, the shadow image has clean and sharp edges. When some gas 01 air or thin foil of metal or mica is introduced in the path of a-rays then image become diffus called scattering. The schemate diagram of Rutherford’s experiment on scattering of a-particles is show Fig. (1.17). Alpha particles from radioactive source radium contained in a lead cavity collimated into a narrow beam with the help of a lead plate having a narrow slit. 5 Scattered particles _ xATOMIC SPECTRA AND MODELS The narrow beam of a-particles are made to fall on a gold foil (about 10~? m thick), beyond which is placed a screen coated with zine sulphide. The o-particles scattered in different directions on striking, the sereen caused tiny flashes which could be viewed and counted Following observations were noted from this | — Incident experiment. a-particles © Most of the c-particles were found to pass through the gold foil without any appreciable deflection + In passing through the gold foil, the different «particles undergo different amount of deflections. A large number of o particles suffered fairly large deflections. « A very small number of a-particles (about 1 in 20,000) was Scattered - particles Fig. 1.18 : 1.35 Nucleus deflected through 90° and occasionally a particle went back along the direction from wi Explanation of a-particle scattering ‘ich it came is deviated through 180° as shown in Fig. (1.18). Rutherford assumed that when an o-particle (carrying positive charge 2e) approaches the positive nucleus (of charge Ze, Z being atomic number) it experience a Coulomb's repulsive force «=(1.66) given by pot ee) _ 2 Ze” Amey 2 Aner? 2 or ieee ai where k= 1 =9x10° Nm2c* 4m ey and €» is permittivity of free space. If the distance r between the nucleus and approaching a-particle is very large, _ the G-particles experience a very small electrostatic repulsion and pass almost undeflected. On the other hand, ifr is very small i.e. a-particle passes close to the nucleus, it experience strong repulsive force and Scattered through a large angle. Occassionally, an o- Particle may be aimed just at the nucleus, the repulsive force will slow down the particle which will NO) °—— B momentarily stopped and returned almost in the urection from which it came. On this basis, he Fig. 1.19ATOMIC SPECTRA AND MopELs 1.36 theoretically calculated the number of a-particles scattered through puele 2 Bie theoretical graph between N(@) and 0 was found to be in full agreement with the graph shown in Fig. (1.19) obtained experimentally. ‘The experimental observations led Rutherford to the following conclusions. ticles passed undeviated, the atom has a lot of empty space in it. (i) Since most of Gi) Since the fast and heavy o-particles could be deflected even through 180°, the whole of the positive and nearly the entire mass of the atom is confined to an extremely smal] centre core. It was called nucleus. (iii) The scattering of different a-particles through different angles was explained on the nuclear model of atom. ER2] RUTHERFORD SCATTERING FORMULA Let us consider a nucleus of radius p. All those incident o-particles aimed to strike the cireumsference of the circle drawn about the nucleus will be deflected through an angle 0. All the a-particles which strike within area mp? (shaded area) will be deflected through an angle greater than @ as shown in Fig. (2.6). The area mp? is called cross-section and denoted by 0. ie. o = np? (1.67) Let us calculate total target area presented by all the nuclei of the foil of area A and thickness ¢. Let us assume single scattering take place i.e. the foil is so thin that in passing through it an a-particle is scattered by only one nucleus. Let W is the atomic weight of the scattering material and p its density. Fig. 1.20 Avogadro's number is No. Then number of atoms per unit volume of the foil (target) N Volume of the foil = At +. Number of nuclei in the foil = nAt Hence target area for scattering by at least an angle 0 = o (nAt) Since the incident beam cannot be aimed to strike any one nucleus in total area is very large as compared to cross section of the nucleus, Therefore anyone incident a-particle that is scattered at angle greater than 0 is givenATOMIC SPECTRA AND MODELS. 1.37 Ng _ o(nAt) Ze? 7 20 Wea so ntannt|—— Fi PAGO) CHOI. N, A cae ine, k| 2 (1.69) (2 o=np”) hh eae ae : wane Ine, B°"D (i.e. p = distance of closest approach) Here Ni is number of c-particles incident on the foil and N, the number of o-particles scattered. This is Rutherford scattering formula. Since in actual experiment, the detector measures o-particles scattered between @ and (@ + d®). The fraction of a-particles, scattered is found by differentiating eq. (1.69) 2 Ze? @ 0 df= —nnt 28 a +=(1.70) if = — nn Es 3] cot = eosec® 0 (1.70) where negative sign indicate that f decreases as 0 increases. Tfwe place a flourescent screen at a distance r from the foil and the scattered a-particles are detected by sentillations they produce, then a-particles scattered between 0 and 0 + d0 will reach a zone of sphere of radius r and width rd9. The radius of zone is r sin @ as shown in Fig. (1.21). Hence area of screen struck by a-particle is dS = (2 mr sin 6) (r d0) = 2nr? sin 6 do Sa! 8 =4nr?sin © cos ® ao nr? sin > cos al ___ Since total number of a-particles incident on the foil = N; -. Number of a-particles scattered per unit area striking the screenise ATOMIC SPECTRA AND MopELs a) cos de cosec® 5 or No= Tee anr® sin 9 cos © do ms? wlio nt Z?e4 int ( --(1.72) RUTHERFORD ATOM MODEL Rutherford gave his atomic model as below : @ Atom may be regarded as a sphere of diameter 10-0 m. The whole of positive charge and nearly whole of mass of the atom is concentrated in the nucleus having a diameter of about 10-4 m, (i) The nucleus is surrounded by electrons. (ii) As atom is electrically neutral, the total positive charge on the nucleus is equal to total negative charge on electrons of the atom. (iv) The electrons in the atom are revolving around the nucleus in various circular orbits. The centripetal force is provided to the electrons by electrostatic force of attraction between electrons and the nucleus. LIMITATIONS OF RUTHERFORD ATOM MODEL Following are the limitations of Rutherford atom model. () According to electromagnetic theory a revolving electron should continuously e energy and hence the radius of its path should go on decreasing and ultimate should fall into the nucleus. However, electrons revolve around the nucleus witho falling in it. Hence, Rutherford atom model cannot explain the stability of atom. (i) Rutherford model cannot explain line spectra of atoms like hydrogen. Because if Rutherford atom model is true, the electrons can revolve in orbits of all possible hence, it should emit continuous energy spectrum, Solved Problems PROBLEM 1. The operating temperature of an indirectly heated filament of a tube is around 1050 K. At what wavelength will it radiate energy. Solution Here = 1050 K, b = 0.002898 mK According to Wein’s displacement law,