Chapter ATOMIC MODEL ES] BOHR ATOM MODEL Postulates of Bohr’s Atom Model 1. An atom consists of a central positive core, called nucleus, which carry whole of the positive charge and nearly whole of mass of the atom. The electrons revolve around the nucleus in certain fixed or permitted circular orbits of definite radii. 3. The permitted orbits are those, in which the angular momentum of an electron is integral multiple of 4 where h is planck’s constant. in Ifm and v are the mass and velocity of the electron in a permitted orbit of radius r, then ply 2.1) where n is called principal quantum number and has integral values 1, 2, 3 The en. (2.1) is called Bohr’s quantisation condition. 4. When electrons revolve in permitted orbits, they do not radiate energy. Such orbits are called non-radiating or stationary orbits. 5. The energy is radiated, when an electron jumps from higher to lower energy orbit and energy is absorbed, when it jumps from lower to higher energy orbit IZ, and B, are the energies associated with orbits of principal quantum numbers n; and ny ‘spectively. If I, > fj, the energy emitted is given by hy = E,- Ey =-(2.2) This eqn. (2,26) is called Bohr's frequency condition.ee ATOMIC Mone, BOHR’S THEORY OF HYDROGEN ATOM Hydrogen atom consists of a nucleus containing a proton carrying a positive charge +e and single electron of charge ~ ¢ revolving around the nucleus in a circular orbit of radius r as shows in Fig. (2.1). ‘The electrostatic force of attraction between the nucleus and the el ron is given by Foe —1_exe Ane * 2 Le’ r Fe= — #-(2.5) ‘ Ameg 7? , where €o is permittivity of free space. If m and v are mass and velocity of electron, then the centripetal force required for electron to move in circular orbit is given by (2.4) The electrostatic force of attraction (F.) between the electron and the nucleus provides the necessary centripetal force (F.) to the electron. Therefore, from eqns. (2.3 & 2.4) 1? _ mv? 4neg Pr 2 or my? = a —_ 4mey r According to Bohr postulate (ie. Bohr’s quantisation condition) nh mor = Bh 2n where n is an integer. nh or veo 2nmr Putting this value in eqn. (2.5), we get n( nh y eta 2nmr 4ney r or mnths 4n’m?,? 2 wre nmr?ATOMIC MODEL or r 7 This eqn. (2.7) gives radius of nth allowed orbit ere: ren? y Thus, for n ny = aREo AE (2.8) \ ame ie Putting the various values we get (6.6210 4x 9x10" x (3.14)? x 9.110! x 1.6 x 10719) or m= 0.53x107!° m=0.53 A +(2.9) This is the radius of innermost orbit (first orbit) called Tl Bohr’s radius. Energy of Electron in Hydrogen Atom ‘The electron revolving around the nucleus possesses kinetic energy. This kinetic energy is given as 1 KE. = >mv 2 1 1 - or KE.=— Using eqn. (2.5), ... 2.10) 2\ 4meq r Potential energy of electron in the field of nucleus 1 (Ge)(-e) PE.= or PE. = (2.11) 4mey 7 Total energy (E) of electron is sum of K.E. and P.E. of the electron. B=KE.+PE. or won| ee 2\4neq r} 4tey 7 2 or ast +-o(2.12) ne qr Substituting the value of r from eqn. (2.7) we get 2 _An’me® 22 z = An mess 8mEq Aneg naa ATOMIC MODEL a +-(2.13) Segtneh® Thus total energy of hydrogen atom is negative and varies inversely as the square of principal quantum number n. rhe re met (2.14) Beye) The allowed values of energy called energy levels of hydrogen atom Frequencies of Radiation and Wave Number Let the electron jumps from higher orbit having quantum number nz to lower orbit having quantum number mi. Let E,, and E,,, be the energies of states m and no respectively. Then a 22 8eq? An? 4 ee ea eae Beq7 h(n? nd The difference in energy is emitted as radiations. According to Bohr postulate hy = Eny - En, h or where v is the frequency of emitted radiation a es Beg” h* ne ny Seegeriee (el 1. or oS KBE hi ln? nb where A is wavelength of radiation emitted and c is the velocity of light ae a pieATOMIC MODEL where =1.0974 x10" mt Ru is called Rydberg’s constant for hydrogen atom. ‘The quantity ue is known wave number (v). It represents number of waves in a unit length. nN ‘The spectrum of hydrogen atom is a line spectra. ENERGY LEVEL DIAGRAM OF HYDROGEN ATOM The energy of electron in the n" stationary orbit of hydrogen atom is given by eqn. (2.14) —me* 8 es n7h? 1_{2n?me*) (4ne)" ( 7p Or (9x10°)’ x2x9.87%9 1x10! x(1.6x1079)* n? x(6.62x10)? 21.76 x10'? ne J " _ __ 21.76 x101® n?x1.6x10* we get the energies of electrons in various stationary orbits as below: eV= Putting n= 1, 2, 3. For 1 13.6 For n=3, Es = -=-151eV 3 For n=4, For n=5,ATOMIC Mone, 26 Exo = For Seal ae Energy (eV) “13.6 Fig. 22 Thus energy of the stationary states increases with increases of principal quantum numbet n. The highest energy state corresponds to n = ~ and has energy E = 0 eV. As n increases energies of the excited states come closer and closer ti values of n, the energy values are so close that they form an ener; the electron no longer remains bound to the nucleus ice. it becomes ogether. For very gy continuum. When n= a free electron. The energy levels of hydrogen and various spectral series are shown in Fig, (2.2). called energy level diagram of hydrogen atom. LIMITATIONS OF BOHR ATOM MODEL © When Bohr's theory is applied to atom with more than one electron, th not agree with experiments entirely. Certain predicted lines do not other words it fails to explain the spectra of multi-electron atoms. Gi) When the spectral lines are stu found to consists of a group of structure of hydroy lines. observe died with a high resolution spectrogra f several lines very close together. This gen lines. Bohr's theory does not explain the fine styATOMIC MODEL [2.7] spectral lines are stronger and others are does not predict anything about the relative ii) It is observed experimentally that some weaker in intensity. Bohr’s theory intensity of spectral lines Ge) Bohr’s postulates look arbitrary. There is no reason for assuming the orbit to he circular and angular momentum equal to intogral multiple of on (@) Itdoes not explain the splitting of spectral lines under the effect of magnetie field CORRECTION FOR FINITE In Bohr’s theory, the nucleus is considered to be at rest because of very heavy mass as compared to electron. But in actual Practice nucleus is having a finite mass and both the nucleus and the electron revolve with a common centre of mass . If the motion of the nucleus is taken into account, then it require some correction in the frequency of spectral lines, 1 coleen M 1 m ——— ee eee Nucleus 12) Electron ‘ ee & $$ x 5» (rn, —___ Fig. 2.3 Let mass of nucleus = M Mass of electron = m Distance of electron from hydrogen nucleus =r Let O is common centre of mass of nucleus and electron. Let x be the distance between the nucleus and centre of mass O, then distance between electron and centre of mass O is (r—x) as shown in Fig. (2.3). For equilibrium condition Mx = m(r -x) es Mx = mr~mx mr . (2.19) x" m+ Also from eqn, (2.18) a Mr 4 Pixon Mri using eq. (2.19)) (2.20) e Cae Gan AG ; Total angular momentum (L) of the atom about the centre of mass is given as | L = Mitw + m(r— x) ( BSBes ATOMIC MODE, | Mr2w mM?r?w (m+ My? (m+ MY? ve using eqns. (2.19 & 2.29) 4 eer Af) (m+ MP? rele = rw M+m L=yrw where ne ( pe | known as reduced mass of electron. | M+m. If we consider nucleus at rest, then angular momentum is given by L =mor = mr2w sev v= rw) Therefore, we see that due to motion of the nucleus, m is replaced by j: and correspondly the energy of the electron in nth orbit is given by 492 ee ee eae a : using eqn. (2.14) Be? 7h’ 4 or En = fet 2.21) [+ Z= 1 for hydrogen] Beg? h? \n which in terms of wavelength is given by a 1 q or v= Ry [3-3] lB Dis 7B where R,, = —->—~ is Rydberg constant considering reduced mass of hydrogen atom. Beq? ch It should be noted that since is somewhat less than m, the wavelength of spectral lines be slightly more in the case of very heavy nucleus (i.e. when nuclear motion is absent). BOHR’S CORRESPONDENCE PRINCIPLE Bohr’s correspondence principle establishes a relation between the results obtained classical and quantum theories, which otherwise are quite different from each other in microscopic world that lies beyond reach of our senses. According to this principle, quantum theory must give the same result as theory in the appropriate classical limit.\ [23] [ATOMIC MODEL ‘ ‘According to classical theory, the orbital frequency of electron in nth orbit is given by 4 f=— (2.28) 4€q7 nh? ‘According to Bohr's postulate (i.e. which is based on quantum theory), when the electron from higher orbit (n) to the lower orbit (71), the frequency of spectral radiation emitted is jumps given by When the quantum number involved are large i.e. ni = n and nz = (n + 1) where n is very large as compared to 1, then fp oeemimened| sla l Bez h? |n? n+)” __ me _[(n+1)?=n Beo2 AF | n2(n +1)” me! Sy Be2h | n(n +1)? 4 (2n+1) or {= ee | ++-(2.24) Beg? h® [23 (2.24) Since n >> 1, so neglecting 1 from (2n + 1) and (n + 1)2, we get met _(2n Mie eaaronl (ae Beg? Ao (n' or Sees | era +=-(2.25) p Comparing eqns. (2.23) and (2.25) shows that both the frequencies (i.e. orbital frequency and Hedteney of emitted radiation) have the same value. Hence classical and quantum theories of ___ hydrogen atom make identical predictions in the case of very large quantum numbers. cuaneenndittons, that quantum physics (i.e. theory) gives the same result as the cqisical physics in the limit of large quantum numbers was called by Bohr, the nines Pondence principle. This correspondence principle has proved to be of great importance pone formation of selection rules. The selection rules limits to a great extent the number of - > sible transitions among the different energy levels in the atoms, hence restricting the number Spectral lines absorbed or emitted by the atom. Seine a(ao ATOMIC Move, FRANCK-HERTZ EXPERIMENT The excitation of an atom by any method from one state to another involves transfer of energy in quanta. This quanta either absorbed or emitted corresponds to some line in the Spectrum of the atom. With this consideration Franck and Hertz in 1914 performed the experiment using inelastic collision of acceler: A direct demonstration of existence atom was fi ‘ated electrons with atoms as a source of excitation, of discrete stationary states postulated by Bohr theory of t provided by James Franck and Hertz, The apparatus used by them is heated cathode C. These electron: Hence, every electron rea re accelerated by potential difference Ve towards the grid G. aching G must have acquired a kinetic energy eVg. After crossing G, the electrons pass through a retarding potential V, and only those electrons reach the anode A which had sufficient energy to overcome retarding potential V,. grid-anode circuit, which is measure the electron current reaching A asa As a result current Jp flows through ‘d by milliammeter (mA). The experiment involves measuring function of accelerating voltage V,, shown in Fig. (2.4). Thermal electrons are emitted from | The experiment was performed with a tube containing mercury vapour. A typical graph between Jp and Vs is shown in Fig, (2.5) Filament Va Eee = yet Maem ee oll Fig. 24 a As V, is increased from zero, the kinetic energy eV, of electron is increased so that more and more electrons cross G and reach A, indicating increase in I,, The rise of current curve as shown in Fig. (2.5), indicating that upto the corresponding value of the acceleratin voltage, the collision of the electrons and atoms are elastic collision and number of electrons reaching A increases with V,. The abrupt fall in I, from M to N indicates that when the kit energy of electron is eV,,, at this voltage these electrons undergo inelastic collisions with close to G so that their kinetic energy after crossing G is smaller than eV,. P shows that the collisions of electrons are again elastic. The electrons again at voltage V,, and after that they gain sufficient energy to from O to M in Further rise from: suffer inelastic overcome V,. Thus collisions continue to be elastic upto V,, (i.e. from N to P). At Va, against most the colli inelastic and there is sudden drop of. J, from P to Q and so on. Hence from above discussion that the c ollisions of electrons with atoms are i some critical potentials V,,, Vay, Vig,ATOMIC MODEL wo | 250 PN 200 | | P | | Ip(ma) 150 M | 100 | 50 x | ° Va, 5 Vep 10 Vag 15 | co Fig. 2.5 The direct evidence from it is that atoms absorb discrete energies eV,,,eVa,,@Vaq>---.. to get excited. The energies other than these are not transferred. Franck and Hertz observed that the sudden fall in Jp is for values 4.9 V, 9.8 V, 14.7 V. So it was concluded that energy levels in the atom are quantized and the absorption and emission of radiation by these atoms are quanta and not continuous. 2] SOMMERFELD’S MODIFICATION OF BOHR’S THEORY The Bohr theory predicted with great accuracy the spectral lines of hydrogen and singly ionised helium atom, but Bohr’s model could not explain ‘fine structure’ of hydrogen spectral lines, The fine structure is splitting of spectral lines into several close, distinct components when observed with instrument of high resolution. It means each Bohr’s energy level in hydrogen atom actually consists of several components Which are close together in energy. In Bohr’s model of hydrogen atom, the electron was assumed to be moving in ctecular orbits, Sommerfeld succeeded in explaining this ine structure by assuming that the electron move in ‘lliptical orbits in general with nucleus at one its foci and “reular orbits of Bohr as the special case. aoe us consider the motion of an electron (mass m, charge e) in an elliptical orbit with leus of charge Ze at one focus as shown in Fig, (2.6). The instantaneous position of electron in Pultt co-ordinates can be described interms of plane polar co-ordinates r and 8, which being “odie functions of time must be quantised separately. Ifp, and p, be the radial and angular momenta of the electron, then according to Wilson- "mnerfeld quantisation rules.ATOMIC Mog, $.p,d0 =n4h +-(2.26) and $.p, dr =n,h +-.(2,37) where no and n; are integers, called ‘azimuthal’ and ‘radial’ quantum numbers respectively According to classical mechanics, the angular momentum of an isolated system remain conserved, then $ p9d0 =noh or Po $ae = nh or Po(2m) = neh h or ne ++-(2,28) Po= Ne 3 (2.28) or Po = Noh where aah Qn If ‘a’ be the semi-major axis and ‘e’ be its eccentricity, then the polar equation of the ellipse is given by Pee) 2.29) r a(l-e*) Differentiating both sides w.r-t. 0, we get =ldr __esin@ Pd aa-e8) ldr __resino or o-oo rd@- a(l-e) Substituting the value of r from eqn. (2.29) on R.H.S of eqn. (2.30), we get ldr a(l-e) | esing or From eqn. (2.27) nh = § p, dr = mudr 6,4 or nh = pmo dr 2 dr)? (0 wnim(S) (3) or nh = $m we) qs ®ATOMIC MODEL = $m 49) (ar)* or toh = $m 2) (*) ao 1-.(2.33) But y= mor = mor? = mr2( 4) di or cs E ai) 2nr? Putting this value in eqn. (2.33), we get _ g Neh (dr)? a =f fe be cane or nh= eee Stig [using eqn. (2.32)] 2m (1 -€cos 6)” =o g © sin’@ or n, macesiinge 2n * (1-ecos 4) As 8 varies from 0 to 2x _ ng te sin? =—2 = 40 2n 5 (1-€cos 6) n, Using standard integration, we get - = x 2n| 5 - ne Baan ae 1 os when n=1then ny (2.35) b= a hence the first orbit is a circle similar to Bohr's orbit. when n=2, n= 1o0r2 = 2, two orbits are possible. 2) and other is an ellipse (1 = 2, ny = 1) Thus corresponding to One is a circle (n = 2, n, when n=3,ny=1, 2,3. Therefore corresponding to n = 3, three orbits are possible. One is a circle corresponding ton = 3, n, = 3 and two ellipses corresponding to n = 3, ne = 1 and ng = 2 as shown in Fig. 2.7),ATOMIC MoDEL where ‘a’ and ‘b’ are the semi major and semi-minor axis of ellipse respectively. According to geometrical properties of the ellipse the quantity (1 — €2) may have vah O and 1. Likewise np and n, may have value 0, 1, 2, 3, .... ete. When (1 — €2) semi-minor axes b = 0) and hence the ellipse reduces to a straight line. It means the electron pass through a nucleus twice during its time period Such type of motion is not possible anc ni, #0. So the possible values of n, = 1, 2, 3, .... ete. where n, = 0, 1, 2, 3, .... ete. Since n,and n, i.e. n, +n =1, 2, 8, .... ete. Therefore, n, +n, =n (an integer) where n is the principal quantum number. Eqn. (2.36) can be written as |e a-e9 = ee fe Ge The tangential velocity of electron can be resolved into two components. (@ radial velocity (¢) along the radius vector - F do (ii) transverse velocity G 9) at right angle to radius vectorToMIc MODEL a =P igi 7 Sees cia Using p, =m 22) & Ea. 2.34) 2m mr lar} | PE. = 2° Ane, r ‘Total energy is given as a. + PE. or Ph Ze mr? 4negr ae! mt bas canna 4 (2.39) Be hn From eqn. (2.39) it is evident that energies corresponding to a given value of principal quantum number n are same irrespective of the value of no. In other words, all the orbits having the same value of n have equal energies. Hence, the introduction of elliptical orbits is no more eful to explain the fine structure of spectral lines. However, Sommerfeld soon after successfully explained the fine structure of spectral lines by considering the relativistic variation of mass of electron. Sommerfeld Relativistic Correction Sommerfeld pointed out that mass of electron varies in the orbit. The velocity of electron in an ellipse is greater when it is near the nucleus and smaller when it is away from the nucleus. Due to the variation of velocity of electron, mass of electron vary in accordance with the special theory of relativity. If the relativistic effect is taken into consideration, the energy of the electron is found to depend on both principle quantum number n and azimuthal quantum number no. In this case energy of electron is given by 262 372 (visi.3 Y pestis Zao S22 (= = (2.40) Beg? wh’ n\n 4n. Ca ee where a =—— is called Sommerfeld fine structure constant. 2eq he 187 Now for n = 1, n= 1 ie. there is only one energy level. For n = 2, no = 1 and ng = 2 i.e. there are two energy levels. Hence the frequency of radiation emitted in the transition of an electron. from nz level to ns level will be slightly different according to the various values of ng which are Possible (i.e. ny = 1, np = 2). The small variation in energy will result in small energy and frequency differences. This explain why a single line of hydrogen spectrum appears as a group of closely associated lines i.e. fine structure of the spectral lines. Selection Rule Sommerfeld theory predicted that the Ha line of Balmer series of hydrogen spectrum (i.e. n2= 8 and n = 2) should consists of six component lines, but experimentally less components were observed. To overcome this discrepancy Sommerfeld’s imposed a restriction on no values for the "fansition known as selection rule.2.16 Selection rule states that only those transiti azimuthal quantum number ng ch anges by + 1 or—1, Le. Ang =+1 The selection rule is of great importance in the theory of atomic spectra. ey LIMITATIONS OF BOHR-SOMMERFELD THEORY Although Bohr-Sommerfel ld theory was quite suecessful in observations on the Structure of atoms and simple spectra, yet it h @_ This theory w Gi) This theory is applicable only singly-ionised helium ete. But it fails when applied to neutral helium atom which has two electrons. Gii) This theor Ge) No logic reason was given for the introduction of quantum numbers. (vy) This theory did not throw any light on the distribution and arrangement of electrons in atoms. y fails to explain the observed fine structure of spectral lines, (vi) This theory could not explain Zeeman effect, Pool PROBLEM 1. Calculate the kinetic energy and potential energy of an electron first orbit of hydrogen atom. Given, e = 16 x 10-19 = 0.53 x 10-1 m, Solution Here e = 1.6 x 109 C, r= 0.53 x 10-0 m Kinetic energy of electron in first orbit, e? _9x10°x(1.6x107!9)2 bla =21.7x 10-9 J = 21.7x10719 jo” = 13.58 eV Ans, 1.6x10719 Potential energy of electron in first orbit