13. Sommerfeld’s Extension of Bohr’s Model In Bohr’s model of the hydrogen atom the electron could move only in circular orbits. This restriction was entirely arbitrary. Moreover, inspite of the striking numerical agreements, the Bohr’s model could: not explain the “fine structure” of the hydrogen Spectrum, The fine structure is a splitting of the spectral lines 'nto several close but- distinct components when observed under| 28 ATOMIC AND MOLECULAR SPECTRA equipment of very high resolution. This means that each Bohr’s energy level should consist of several close components. Sommerfeld, in 1916, in an attempt to explain the fine structure extended Bohr’s model by assuming that the electron could move in elliptical orbits also. Following Sommerfeld, let us consider the motion of an electron (mass ™, charge —e) in an elliptical orbit, with nucleus (charge Ze) at one focus (Fig. 9). ; Fig. 9) A sane instantaneous position of the electron can be de terme of the plane polar coordinates rand 0, But 7 and 0, functions of time, must be quantised separately Sommerfeld rules). ) “) a 2 wae potential and kinetic energies of the electron” 7 ez ‘ r and K=tmP+ re, here> atthe paren Welocity of the Seton a The radial and angular momenta of or The total energy of the el7 AW) 0 This isthe differential equation of the (clip cal) orbit of the electron moving about a centre of force (nucleus). TO } {ts axes, we write the polar equation of an ellipse : } 1 1 l-ecos 0 (vi) 7 ie } semi-minor to semi-major axis). where VI—e)= 2 (ratio of jation of r with respect 10% Taking logarithmic different we get 1 das 1 cam pegs @ sles 1 dr sin 0 or ze Tee Ufrom ea. (Wil or (¢ i Now, from eq. (vi), or or sin? gp=e—e cos? O=' eae ee (T—ec0s 8) a This is identical with eq. (v). rin them, we have E and But 1—-&=b'/a*‘ATOMIC AND MOLECULAR SPECTRA 30 mZé 2. - Gx) and fan as Dividing (viii) by the square of (ix), we have amE pet mZte'|pe a mZ2e (b/2") , u@ or E=— 7 Eq. (ix) gives ie de®. ° pe the energy and . (x) and (xi) give respectively elliptic orbit in terms of angular momentum of Let us now introduce quantizati feld quantum conditions to each of the have f dram as Po do = kh, where 7, and k are integers called the ‘radial’ and “azk tum numbers respectively. The second int because according to classical mechanics, p, of any isolated system is constant. Thus, ‘over a complete cycle, Qn os or The angular momentum of at the last expression may be This restriction on the Bohr circular orbit th To evaluate theBOHR-SOMMERFELD THEORY OF HYDROGEN ATOM. 31 Pe dr e 2 40 ea Pe=me? 7 ar and dr = aii do Pedr =p, (+ %) 40 2 sin? @ 7 Te do. [from eq. (vii)) ) becomes Hence the integral in oa ( sin? 6 oat ~ Le | The value of the definite integral is 2 (aes -1) . So we have \-¢ onary -t) = But p, = £2, as obtained above. or or or But /(I—e) = 4/2.eee 32 ATOMIC AND MOLECULAR SPECTRA The radial quantum number n,, however, takes the zero value for which the orbit is circular. That is a, = 0,1, 2,3,. Therefore, n can take on the values : Wee 142,34; su Fora given value n, the k can assume only the values kee 1.2) 3, on, The eq. (xv) now becomes 5 k E=# This is the quantum condition for the elliptical orbits. Out o the classi ically possible ellipses, the electron can move onl orbits for which the ratio of the minor to the major ng two integers, k and n, We can now write the quantised values of the total energy. E the electron and the semimajor and semiminor axes a: which give the size and shape of the elliptical orbits, Applying the quantum conditions Po e and 4 €q. (x) and (xi), we get % B= — m2 =-=- whe o = aemZet = 07% k nk and b=a re = % Zz z ; where ap is the radius of the smallest Bohr The energy expression, given same as for the Bohr’s circular orbit, electron still depends on the princips independent of the azimut! The size and shape determined by eq. (xviii) predicts that for any quantised orbits for the el Let us consider the fir: is is a circular orbit a tie elaBOHR-SOMMERFELD THEORY OF HYDROGEN ATOM 33 For n=2, we have (i) k=2 sothat a=4ay) b=4d } 4) (ii) kK=1 so that a=4a) ce} > b=2ay mae ‘Thus for n=2, we have a Bohr’s circular a ned orbit of radius 4a) , and an. elliptic orbit 18 with semiemajor axis 4p and semi-minor Fig. 11) axis 2ap (Fig. 11). For n=3, there are three types of possible orbits : () k=3 so that a=9a, } b=9aq (ii) k=2 so that a=9a, on (iii) K=1 so that } _ b=3my J. Thus out of the three possible orbits, one is the Bohr’s circular orbit of radius 9a) , the other is an elliptical orbit of i axis 9a) and semi-minor axis 6d), ani the third is an elli ‘orbit with semi-major axis 9a) and semi-minor axis 349 (Fig. 1 We see that oorreal A 1 number n, er se dia le are es radius of thep MOLECULAR SPECTRA ’ aitowed by the electron 3. vy aitferent paths oy, given m, the total : vie very Silfee orbits fas that Sommerfeld’s This mea? energy levels and ‘ orbits cha- But, despite ir pont 2 the y > ie. movin tcciun nS adds *° he several coe Boction of cMPUTT. gine Siructure. Uh to be ‘degenerate’. hence fails to explain valuc of energy at a racterised by i and i values he value To designate an OF. I, fr Bs oe ig as of n is followed by One of te aoe 5 Fr opie, encueete n=3, hel 23. 4 respectivelY: | "3, pad OS 3p. It is seen that Peles entipa 2s, 38200 thet "=" ¢ elliptical im any family of the s-clectron orbit lowest k) de it Orbits having same major ax!s ( P sa 14, Sommerfeld’s Relativistic Correcti ni Sommerfeld removed, the degeneracy 18 the electron moving in ¢) ducing the relativistic val electron in the innermost Or) hyor less, Although, this would give a relativistic ¢ energy only of the order of 10-*, but it is splitting of energy levels required to exp! structure of hydrogen spectral lines. ae In an elliptic orbit the velocity of & largest near the perihelion, The actual correction depends upon the average which, in turn, depends on the ellipticity of that the correction is different foc diffe and thus the degeneracy is removed. Using the relativistic exoression for the electron, K=mgc* a 5] ~ of the electron, (7e=we De of the electron as ae JL 1 dtecosys aes where ¥ ( n=l, 2, 3,...-- These two equations give °c?) edn The number of revolutions of the electron in the orbit per second is ome S a : Substituting the known values of jm (OTT X10 cm = 82x 10! sec, Fence the revolutions of the electr = (82x 10") x 107 2. The series limit wavelength o spectrum is 3646 A.