> O » Atomic > Molecular © Rss LaserCONTENTS pe. Chapter Page 1, Introduction | 2. Bohr-Sommerfeld Theory of Hydrogen Atom 6 3. Quantum Mechanics of Hydrogen Atom : Angular Momentum and Parity 48 4. Magnetic Dipole Moments, Electron Spin and Vector Atom Model 7 5. Spin-Orbit Interaction : Hydrogen Fine Structure 90 6. Identical Particles : Pauli’s Exclusion Principle 103 7. Helium Atom and its Spectrum i 8. Multi-electron Atoms : Hartree’s Field : Atomic Ground States and Periodic Table 121 9. Spectroscopic Terms : L-S and j-j Couplings 138 10. Spectra of Alkali Elements 169 11. Spectra of Alkaline-Earth Elements and Complex Spectra 185 12. Zeeman Effect and Paschen-Back Effect 201 13. The Stark Effect 226 14. Hyperfine Structure of Spectral Lines 232 15. The Breadth of Spectral Lines 250 16. X-ray Spectra 255 17. Types of Moletular Spectra and Molecular Energy States 5 275 18. Pure Rotational Spectra 284 19. Vibrational-Rotational Spectra 302 20. The Raman Spectra 336 21. Electronic Spectra : Franck-Condon Principle 349 22. Isotope Effect on Electronic Spectra 380 23. Fluorescence and Phosphorescence 388 24. Classification of Molecular Electronic States « 393 25. Symmetry Properties of Rotational Levels : Nuclear Spin and Intensity Alternation 26. Coupling of Rotational and Electronic Motions : Types of Electronic Transitions 416 27. Co-relation between Atomic and Molecular States : Building-up Principle 445 400 28. Molecules and Chemical Bonds : The Stability of Molecular States 474 29. Continuous and Diffuse Molecular Spectra : Dissociation and Predissociation 504 30. Temporal and Spatial Coherences 523 31. LASER : Einstein's Coefficients and Light Amplification 531 32. Types of Lasers : Characteristics and Applications of Lasers 541-5551 Introduction | Spectroscopy is that branch of Physics which deals with the observation and interpretation of radiation emitted and absorbed by atoms and molecules, and throws light on their structure. It provides information not only about the arrangement and motion of the outer electrons (optical spectroscopy), but also about the inner electrons (X-ray spectroscopy), and about the angular momentum, magnetic moment, distribution of charge and magnetism of the nucleus (study of hyperfine structure, nuclear magnetic resonance, ete.) It was Sir Isaac Newton who originated spectroscopy by showing that a prism refracts blue light more than red light, thus forming a band of colours known as ‘spectrum’. Today, we know that the visible spectrum is a very small part of the broad electromagnetic spectrum ranging from the y-rays to the radio-waves. The wavelength and the frequency v’ of a monochromatic wave are related as VA=o, il) where v is the phase velocity in the medium. The phase velocity v of an electromagnetic wave in a medium is related to the phase velocity c in vacuum by ve 7, where [J is the refractive index of the medium with respect to vacuum, The frequency of a wave remains unchanged as it propagates through various media, Hence, for vacuum, eq. (i) may be written as V Doae = and for a dispersive medium (say, air) we write ! hair = Pair = V Deir = Pair = Thus, the frequency of an electromagnetic wave may be expressed as c ¢ ver-= Tee Hi Mair gth in the visible part of the spectrum is measured in A (angstrom units), The wavelen; which is 1A = 10%cm = 10m = 10°' nm (nanometer). Infra-red wavelengths longer than 10,000 A are measured in microns (1), which is 1p = 10-tcm = 10°°m = 10°A. A smaller unit is millimicron (mp), which is Imp = 10°7cm = 10°m = 10A. For the analysis of spectral lines, frequency is more fundamental than the wavelength because the frequency of monochromic light does not alter in different media. However, frequency is numerically very large. For example, the frequency of visible light of wavelength 6000.A is‘Atomic and Molecular Spectra : Laser ec, 3x 1s” 25x 10's"! (her). Aree 6000 x 10m Therefore, in spectroscopy, ‘wave numbers’ (the number of waves ber meter of per cm) rather than frequencies are usually employed. The wave number Vv is the reciprocal of : . wavelength in vacuum, and is expressed in cm v= a mt orin m= To find the wave number for a wavelength measured in air, we must first convert the wavelength in air to the wavelength in vacuum by multiplying it by the refractive index of air for that wavelength, and then take the reciprocal value. Standard wave number tables are available for this computation. ‘After Newton, Joseph Fraunhofer in 1814 observed dark lines in the solar spectrum, Soon after, Kirchhoff and Bunsen found such dark lines, ‘and similar bright lines, in the spectra of stars and laboratory flames and sparks. This brought into picture two types of spectroscopy, the ‘emission spectroscopy and the absorption spectroscopy. reer picees of apparatus required in the study of spectroscopy area igh sous, a dispersing device and a receiver (eyepiece of camera). The ways of producing light for spectroscopic studies are ‘temperature radiation’ and “juminescence’ (which includes electroluminescence, chemiluminescence, fluorescence and phosphorescence). In temperature radiation, the atoms and molecules of gases are excited by collision with other atoms and molecules at high temperature. The excited atoms and molecules emit light. This occurs in flames and electric furnances. In electroluminescence, atoms or molecules are excited by collision with electrons or ions ecelerated in an electric field. This occurs in all kinds of electric discharges (arcs, sparks and Geissler tubes). In chemiluminescence, energy is set free in a chemical reaction andis converted into light. This phenomenon takes place partly in flames. Photoluminescence (fluorescence and phosphorescence) results from excitation by absorption of light. vr igh from the source is focussed on the enance sit of a spectrograph. Nt disperses it and forms an image of the slit in its focal: plane. Images in different wavelengths occur at different points along the focal plane. The succession of images of the entrance slit is called the ‘spectrogram’. The main observations in the spectrogram are as follows : (i) Monoatomic gases (when heated to incandescence) give distinct bright emission lines; polyatomic gases give bands composed of closely spaced lines; and very dense gases or solids give continuum. (ii) A continuous spectrum seen through a cool gas shows absorption lines of bands. Th’s means that a cool gas absorbs from continuous light those very wavelengths which emmuts when heated. (ili) The positions (wavelengths) of spectral lines are charactensstic of the atoms o molecules which produce them. (iv) The intensity of spectral ines grows as the concentration of atoms increases: pee spectral lines vary with the temperature of the source. a peciral line may serve as a standard of length. In 1907, the red line (6438 A) was adopted, Then, it was replaced by the green line (5460 A) of mere) ws isotope (Hg'”*), and in 1960, the orange li i ) , ge line (6058 A) of krypton isotope (KF chosen. The wavelength of krypton orange line in varus is pton iIntroduction Yeoc = 6057802106 A. As reliable light sources and wavelength standards became available in the second half of the 19th century, spectroscopists began to note regularities in the spacing of spectral lines. In 1870's, Liveing and Dewar noticed that the spectral lines of various elements could be grouped into distinct ‘series’. In each series, the spacing and intensity decrease regularly towards shorter wavelengths, until finally it becomes impossible to distinguish the individual lines (series limit). The various series in complicated spectra overlap. The simplest is the hydrogen spectrum. Its visible part shows a single series (Balmer series) which starts at 6563 A in the red and proceeds toward a limit at 3646 A in the violet. Besides this, there is a series in the ultraviolet (Lyman series); and a few series in the infra-red and far infra-red (Paschen, Brackett and Pfund series). Balmer, in 1885, discovered a formula predicting the wavelengths of all the lines of the Balmer series, which is A = 3646 2 so sn BAS ce n-4 Subsequently, Rydberg found that Balmer’s formula was a special case of the following more general wave-number formula for hydrogen ; 1 1 v ta a7 iF where nj and m are positive integers (n2 > mj) and Ry is the Rydberg constant for hydrogen. From recent spectroscopic data, the value of Ry is known to be 109677576 cm™' (or 10967757-6m™'). To obtain Balmer's formula, we set m = 2; and ny = 3,4,5,.... The series limit is derived by putting np = =. The above formula predicts all known series of the hydrogen spectrum. We thus conclude that the wave numbers of the hydrogen lines can be expressed as differences of two ‘terms’ of the form * The next simplest spectra are of the ‘monovalent’ atoms of alkalis Li, Na, K, ... which form the first column of the periodic table. The elements share many chemical properties and this is attributed to the presence of a single ‘valence’ electron in the outermost orbit. Spectroscopically, a typical alkali spectrum can be grouped into four distinct series. The strongest is the ‘principal series’ which, with the exception of its first member, lies in the ultra-violet. The other two, sharp and diffuse, series lie in the visible part, while the fourth one, the fundamental series, lies in the infra-red region. Rydberg represented the wave numbers of the lines of a particular series by the formula 1 1 (m - Ay? (m ~ 42 J where Rq is the Rydberg constant for a particular element A ; n; and ny are positive integers, and A, and A, are quantum defects (<1). The integer mj is fixed for the particular series, while 2 is a variable integer. ‘The lines of an alkali spectrum, under high resolution, show a fine structure and are termed as ‘doublets’. The fine structure becomes more pronounced in the heavier elements. Again, we find that the wave numbers of the lines can be expressed as difference of RZ (n - ay veRZ two ‘terms’ likeIntroduction 5 a” From this we draw a final conclusion : “The number of valence electrons determines the qualitative character of a spectrum (that is, the number and types of series), whereas the net atomic charge affects quantitative details (that is, the wavelengths of lines in series).” Wave number Units : The wave number units are commonly used by spectroscopists as a measure of energy. When a single particle (atom or molecule) emits light, the emitted light quantum will have an energy given by, Eshv, (Planck's photon theory) where A is Planck's constant and v’ is the frequency of emitted light. But v’ = cv, where v is the ‘wave number’ of the emitted light. Therefore, Eshev. Substituting the known values (upto 4 significant figures) of the universal constants hand, and taking v = 100m™' (= 1 cm™'), we have E = (6-626 x 1073s) (2.998 x 10° ms") (100 m7!) = 1986 x 1077. Thus Lem"! = 1986 x 10°” J/molecule wf) Now, | mole contains 6023 x 10° molecules (Avogadro's number), Therefore, we can write (1.986 x 10° J/molecule) x (6023 x 10” molecules/mole) 11-962 J/mole. Again | cal = 4-186 J. Therefore 1 + 11-962 J/mole 4-186 J/cal ‘Thus 1cm™! = 2-858 cal/mole = 2-858 x 10” keal/mole. +B) ‘We can also obtain interconversion between electron-volt and cm. We know that 1eV = 1-602 x 107"? J/molecule . 1.986 x 10" J/molecule 1-602 x 107"? 3/(molecule-eV) or Lem! = 1239 x 10° “eV. AR} 1.602 x 107" J/molecule 1 Converse! V eg x Lem yy 1eV = 986 x 10° J/molecule = 2-858 cal/mole. or 1eV = 8066cm (DY From relations (C) and (B) : 1.239 x 10° eV = 2-858 x 10°* kcal/mole 2.858 x_ 10°? kcal/mole 1.239 x 10°* or 1eV = 23-06 kcal/mole. or leVe2 Bohr-Sommerfeld Theory of Hydrogen Atom ———————————————————————:._ OOMw6>< 1. Atomic Spectra When an atomic gas ot vapour is excited, say by the passage of an electric currrent through it, the emitted radiation after being dispersed by @ suitable spectrometer becomes concentrated at a number of discrete wavelengths. Each of these wavelength components is called a ‘spectral line’, and the whole family of lines is called a ‘line spectrum’ or ‘atomic spectrum’. Investigation of the spectra emitted from different kinds of atoms shows that each kind of atom has its own characteristic spectrum, that is, a characteristic set of wavelengths. This makes spectroscopy 4 usful tool for chemical analysis of an unknown substance. ‘A characteristic feature of line spectra is that the spectral lines can be grouped in one, ‘or more, series in which the separation and intensity of lines decrease regularly toward shorter wavelengths. For example, in the line spectrum of hydrogen atom is observed a serics of lines whose , ° separation and intensity # o< = s ot decrease in a_ perfectly 3.6: 3 regular manner toward + a shorter wavelengths, and t the series converges to a | limit at about 3646 A | (Fig. 1). The line with thee Ha Hy He Hoe longest wavelength, 6563 A, (SERIES LIMIT) is designated Hg, the (BALMER SERIES OF HYDROGEN) next of wavelength 4861 A (Fig. 1) is designated Hg, and so on. Balmer, in 1885, discovered an empirical formula representing the wavelengths of the hydrogen lines. His formula is A, 2 a-4 for Ha , Hy «Hy... ines respectively. The series is therefore named where n = 3,4, 5, as ‘Balmer series’. The formul i ; Byabens om a is more generally written in the following form, which is due to Ritz and wt 1 1 y ne hala B)i ne a4, Balmer ® a ABohr-Sommerfeld Theory of Hydrogen Atom 7 where v is the wave number of the line and Ry is the Rydberg constant for hydrogen and has the experimental value Ry = 109677576 mm! = 1.097 x 10’ m=! (= 1.097 x 10°cm™'). The Balmer series contains only those spectral lines of hydrogen atom which oceur in the visible and near ultra-violet parts of the spectrum. The spectral lines im the ultraviolet region form the ‘Lyman series’ which is specified by the formula van mal - Lyman In the infra-red, three spectral series have been found which are specified by the formula vege kiss - ame hse Paschen veto =p} ae ser Brackett veqom(s - afassne Pfund Similar regularities are found in the spectra of more complex atoms. The series formulae for those spectra are of the same general structure as for hydrogen spectrum. 2. Bohr’s Postulates Niels Bohr, in 1913, developed a model of atomic structure which was in accurate quantitative agreement with the observed hydrogen and hydrogen-like spectra. This model is based on certain postulates which are : (i) An electron in an atom moves in @ circular orbit about the nucleus under the influence of the Coulomb attraction between the electron and the nucleus, according 10 the laws of classical mechanics. This postulate bases Bohr’s model on the existence of the atomic nucleus and embodies some of the ideas concerning the stability of the nuclear atom. (ii) Out of the infinite number of orbits which would be possible in classical mechanics, it is only possible for an electron to move in an orbit for which the magnitude of its orbital angular momentum ’ is an integral multiple of h/2n, where h is Planck’s constant. That is, h et IDt= 33 n= 1,2,3,.00- This postulate introduces quantisation. We shall sce that the quantisation of the orbital angular momentum of the atomic electron leads to the quantisation of its total energy. (iii) The electron, in spite of its accelerated motion, does not radiate electromagnetic energy while moving in an allowed orbit. ‘Thus, its total energy remains stationary. This postulate removes the problem of the stability of the electron moving in a circular orbit, due to the emission of electromagnetic energy as demanded by classical theory. (iv) Electromagnetic radiation is emitted if an electron, initially moving in an orbit of total energy Ej, discontinuously changes its motion so that it moves in a lower orbit of total energy Ey. The frequency v’ of the emitted radiation is given by 2-4. ¥ ha Atomic and Molecular Spectra : Laser Ato and Molecular Spectra : Laser This postulate is closely related to Einstein's postulate (E = h V) that the frequency ot Avantum (photon) of electromagnetic radiation is equal to the energy carried by quantum divided by Planck's constant A a ostulates mix up the classical and non-classical Physics. The electron moving in a Circular orbit is assumed to obey clasical mechanics, and yet the non- 1). Now, as a common tendency of all physical systems, the atom emits its excess energy and Teturns to the ground state. This is accomplished by a series of transitions in which the electron drops to states of successively lower energy, finally reaching the ground state. In ¢ach transition, electromagnetic radiation is emitted with a wave number determined by ©4. (vii). For example, if the electron is excited to the state n = 7 and drops successively through the states n = 4 and n = 3 to the ground state n = |; then three lines are emitted with wave numbers given by eq. (vii) for n, = 7 and ny = 4 0, = 4 and ty = 3; and n, = 3 and my = 1. For hydrogen Z = 1; so that eq. (vi = Rez ; | vii) ala = 3 This is identical with the series formula for the various series of the hydrogen spectrum, if Ra = Ry. According to the Bohr modelAtomic and Molecular Spectra : Laser 12 me Re geile Taking the known values of m.e.tysh and © upto six significant figures, We obtain R= 1.09737 * io. which is in good agreement with the experimental value of Ry five known series ofthe hydrogen spectrum According (0 the Bohr model, each of the in which the electron drops to 8 cel yy arises from a set of trat srtain final state ny Balmer series Paschen series Brackett series n, = 6.7 Pfund series (Fig. 4). The transition .d by an arrow going from an initial ; Ba ied in terms of the energy-level diagram fine of a series is indicates ny ‘These series are illustrat giving rise to a particular Ue LA PA’ SCHEN BALMER —> V(WAVE NUMBER) (Fig. 4)Bohr-Sommerfeld Theory of Hydrogen Atom 13 quantum state n; to the final quantum state ny. Since the distance between any two energy levels is proportional to the difference between the energy of the two levels, the length of any arrow is proportional to the wave number of the corresponding spectral line. The theoretical explanation of Balmer series was a great success for Bohr’s theory. The success was particularly impressive because the Lyman, Brackett, Pfund series had not been discovered at the time the theory was developed by Bohr. The existence of these series was predicted by the theory, and the series were observed experimentally in 1916, 1922, 1924 respectively at the predicted positions. 4. Unquantized States and Continuous Spectra In the spectrum of hydrogen, a continuous band is observed starting at the series limit and extending some little distance to higher wave numbers (or shorter wavelengths). This continuum is explained as due to ‘unquantised’ hyperbolic orbits on which the electron can move (Fig. 5). It can be shown from classical electrodynamics that an electron moving about a nucleus in an hyperbolic orbit has a positive energy. Further, since the orbits are unquantized, all possible values of energy are possible. From an unquantised orbit, the electron can pass into or ‘one of the quantised orbits with emission-of radiation. If the transition takes place when the electron has a velocity p and is ata distance r from the nucleus, the total initial ze 4neyr (Fig. 5) energy (kinetic + potential) is im v= 3 while moe + Hence, by Beh? Fa a Bohr’s postulate (which applies to all emission and absorption processes, whether the orbits are quantized or not) the frequency V’ of the emitted radiation is given by 2 Zé + 225(5) the final energy (when it reaches a quantised orbit n) is — 1 ava qm’ ~ Geer” segh (ar This frequency is greater than that arising from wansitions between orbits, both quantised. Hence, the spectrum will lie beyond the series limit. Since v and r can take all values, the spectrum will be continuous. These transitions can be shown in the energy-level diagram by arrows starting from any point in the continuum (which is above the energy level n = e) and ending on any quantised level. 5. Bohr’s Model and Absorption Spectra When a beam of continuous light is passed through a glass cell containing hydrogen gas in the atomic state and then sent into a spectrometer, a set of dark lines on a bright background is observed. This is the absorption spectrum of hydrogen. In terms of quantum theory, the incident light is considered to be a beam of quanta (photons) of all possible energies. According to Bohr's model, only those quanta are absorbed by the hydrogen atoms whose energies correspond to transitions between the allowed energy levels of the atoms. Hence discrete dark lines appear against the continuous background. The process of absorbing radiation is just the inverse of the emission process, au * ~xe the absorption lines have exactly the same frequencies as the emission lines14 Atomic and Molecular Spectra : Laser ME The dark lines in the absorption spectrum are never completely black, but only appear so by contrast with the bright background. The reason is that the atoms which are excited by absorbing radiation, re-radiate the absorbed energy almost atonce, but these photons come off in random directions with only a few in the same direction as the origional beam of continuous light. No Balmer Lines in the Absorption Spectrum of Hydrogen : It is observed that for every fine in the absorption spectrum there is a corresponding line in the emission spectrum of the substance. The reverse is, however, not true, Only certain emission lines appear in absorption. The reason is that normally the atom is initially in the ground state n = 1, and so absorption transitions can occur only from n = 1 10 n> 1. Therefore, lines of only the Lyman series appear in the absorption spectrum. However, in absorption spectra of certain stars, lines of the Balmea series have been observed. This is due to the fact that, on account of the high temperature of the stellar atmosphere, a sufficient number of hydrogen atoms are in the first excited state n = 2. We can, however, estimate the temperature of hydrogen gas in the atomic state at which the Balmer series will be observed in the absorption spectrum. According to Boltzmann probability distribution, the ratio of the number nz of atoms in the first excited state to the number m, of atoms in ground state, in a sample in thermal equilibrium at temperature -T is m oft m7 gat where k is Boltzmann's constant, = ee ET k = 138 x 10°" I/K = 862 x 105 eW/K. Now, for hydrogen, we have E, = — 13-6eV, E, = - 3: WeV,andso E, - E, = - 13-6 + 3-39= — 10-21eV ME wom evsnsa x 0 ev/KyT _ ete 10 KT. ny ~ It is apparent that a significant fraction of the hydrogen atoms will initially be in the n = 2 state provided T is of the order of 10° K. Resonance Line : When an atom in the ground state is excited to a higher state by the absorption of monochromatic radiation, it can fall directly back to the ground state, or after —e other lower states. Therefore, the substance gives emission line of the 5 juency as al , and also lines of frequenci i called ‘atomic fluorescence’. of smaller oe emai If, however, hydrogen gas is illuminated with monochromatic radiation corresponding to the first line of the L; i is radiation wi i Sr epee ets ground state 6. Correction for Finite Nuclear Mass Let us now drop the electron and oo meee assumption that the nucleus is infinitely heavy compared 10 fixed in space. Infact, the nucleus has a finite mass, and tneBohr-Sommerfeld Theory of Hydrogen Atom 15 electron and the nucleus both revolve about their common centre of mass C (Fig. 6) which remains fixed in space. We must make correction in Bohr theory for the finite mass (or motion) of the nucleus. ELECTRON c ™ { ) (Fig. 6) Let m be the mass of electron, M the mass of nucleus, and r the distance between them, Let x be the distance of the electron from the ceatre of mass C. The distance of the nucleus from C will be (r — x). Since the system is in equilibrium, the moments of mand M about C will be equal. That is, mx =M(r— x). This gives Since both the electron and the nucleus revolve around C with the same angular velocity @, the total orbital angular momentum of the atom, L, is the sum of the angular momenta of the electron and the nucleus. Thus L=mvo+M(r-xo wee mie Tot ne docun at (m + My (m + My _mM(M+mPro (m + My" mM =e x= Let us write mM _ m+M~* where 1 is called the ‘reduced mass’ of the electron because it is less than m by a factor 1/| ( 1+% } Then, the total angular momentum of the atom about the centre of mass is L=pPo. To take nuclear motion into account, Bohr modified his second Postulate and said that the electron can move only in those orbits for which the angular momentum of the atom is an integral multiple of k/2x. Thus, from this quantisation condition, we have nh 2 —- bra= ssie Atomic and Molecular Spectra : Laser nh ing wi we wore, (2? = ra) In the absence of nuclear motion, the corresponding equation is A comparison of the last two equations shows that a replacement of m by 1 in Bohr's derivations takes into account the finite mass of the nucleus. ‘Tha energy of cha lectron ia isn cable of one-slecton stom mew 52 - BCS) BqQh a Since 1 is slightly less than m, the electron energies are slightly less negative than if the nucleus were at rest (that is, infinitely heavy). The wavelengths of the spectral lines computed on the basis of the above energy equation are slightly larger than those corresponding to an infinitely heavy mucleus, and agree more closely with the experimental values. 7. Variation in Rydberg Constant due to Finite Nuclear Mass ‘The finite nuclear mass causes a slight variation in the Rydberg constant from atom to atom. The Rydberg constant for an atom having an infinitely heavy nucleus is ‘4 me’ x Beghic and that for an atom having a nucleus of mass M is ‘ y= HE, 2 Sth mM m where he eM 1+3 4 Bee oe e148 m ty It Thus, Ry is less than R. by a factor —! 7 tnd it liferen for diferent aims M depending upon their nuclear masses. Taking the known values of m,e, &,h and c, upto six significant figures, we obtain Ry = 109737 x 107m! = 109737 m7! For the most extreme case of b a 1 vydrogen, 47 = ——.. The Rydberg constant for hydroget is worked out to be Mie “ / Ry = 109677 cm=!, ‘Thus, Ry is less than R, by about one part in 2000, The variation of Rydberg , is shown in Fig. 7. Constant from element to clement against the mass numbet H! and -H?, With increasing ™*Bohr-Sommerfeld Theory of Hydrogen Atom 7 109740 109700 109680 — MASS NUMBER (Fig. 7) From Bohr’s model, the expression for the series spectra of one-electron (hydrogen-like) atoms, assuming infinitely heavy nucleus, was obtained as 1 14 v=>=RZ/-5 - -5)- Cad nj Taking into account the finite mass of the nucleus, this must be written as 1 1 1 vege Ree - +). n nj For hydrogen (H), Z = 1. Hence writting Ry instead of Ry, the expression becomes 1 1 1 vey = alo - wf} neon For singly-ionised helium (He”), Z = 2, and so 1 L 1 vag 4Re oo 7? For doubly-ionised lithium (Li™*), Z = 3, and so rhonda) wien yon For triply-ionised beryllium (Be*), Z = 4, and so 1 V= T= 16 Ree (a a The spectral lines of these atoms have been found at the calculated positions. It is found that Bohr’s theory corrected for finite nuclear mass agrees with the experimental data to within 3 parts in 100,000. The difference in the Rydberg constant for hydrogen and (ionised) helium can be utilised to compute the ratio of the mass m of the electron to the mass My of the hydrogen nucleus (that is, proton). Determination of m/M,y : The Rydberg constant for hydrogen atom is given by Re wai) Ru = 5 (n/My)’18 Atomic and Molecular Spectra : Laser where R.. is the Rydberg constant for an infinitely heavy nucleus, m & the mass of — and My is the mass of hydrogen nucleus (that is, mass of proton). Similarly, the Rydberg constant for He’ is given by ea Re “T+ (7M) * where My, is the mass of a helium nucleus. Since the mass of a helium nucleus is very nearly equal to four times the mass of a hydrogen nucleus (Mye = 4 My), we write = —— Re ei) 1+ (n/4My) Rite Rue Dividing eq. (i) by (i), we get Ra = 1 + (m/4My) Rue 1 + (m/My) m or (1+) u(t + aa 1 or Wage ~ GRud = Rue ~ Re am _ Rie = Ra vr Mn Rue 4 \ Rae and Ry can be found by measurements of way hydrogen spectra. Hence m/My,, the ratio of the mass of electron to the mass of proton (that is, hydrogen nucleus) can be determined, Further, if e/My (specific charge of hydrogen ion or the charge required to liberate 1 gram-equivalent of any substan ce, known as Faraday constant) is given, we can evaluate the specifi charge of electron ( }: velengths in the series of helium and e m © e/My m~ m/My €/Mry is 96500 coulomb/gram and m/My is 1/1836, fe Sse = 177 x 10'C/g = 1.77 x 10" Crk. 8. Discovery of Heavy Hydrogen The variation of Rydberg constant with the finite iia discovery of deuterium ayy ‘hy (finite) mass of the nucleus resulted in fucleus has a mass almost ydrogen). Deuterium is an isotope of hydrogen; its exactly double that Rydberg constant for deuterium is y of ordinary hydrogen, Therefore, the fe slightly greater than that for hydrogen; as shown below : onl 109737 cm=! Ra m — = 109678 cm! 1+7- teat Mn 1836 and Rp = Fe = 109737 cm! 14" 1, 17 " 109707 cm”! 1+ aot 21836Bohr-Sommerfeld Theory of Hydrogen Atom 19 Consequently, the wavelengths of the spectral lines of deuterium are slightly shorter than those of the corresponding spectral lines of hydrogen. The H, line of deuterium, for example, has a wavelength of 6561 A, while that of hydrogen is 6563 A; a small difference but sufficient for the identification of deuterium. The general nature of the two spectra is, however, exactly same because atoms of both hydrogen and deuterium have the same electron structure. Urey, in 1932, photographed hydrogen spectrunf by means of a large concave grating, He observed that each hydrogen line was accompanied by a very faint line slightly on the short wavelength side. He measured the wavelength difference and attributed the faint line to some heavier isotope of hydrogen. This isotope is now known as ‘heavy hydrogen’ or ‘deuterium’. The relative abundance of deuterium in ordinary hydrogen was calculated to be approximately | part in 5000. This was taken another success of Bohr’s model. 9. Comparison of H and He* Spectra Pickering, in 1897, discovered a new series in €-Puppis star which was first attributed by Rydberg to some form of hydrogen since it could be represented by a formula similar to the Balmer’s formula for hydrogen. Later on, the experimental work of Evans, Fowler and Paschen showed that this series arises due to ionised helium. Putting Z = 2 and Rye for the Rydberg constant in the Bohr's formula, all the four series of ionised helium can be represented as : 1 1 1 vag n thal os “a Each series arises from a set of transitions in which the electron drops to a certain final state ny: may Pickering series n= din Fowler series La ; ; x - 2.3.4, } Lyman series in extreme ultraviolet A comparison of the Balmer series formula for Ry 1 1 1 y= mula - wh y= 34,5, coe a (= nj with the Pickering series formula for He* 1 1 1 vapr etal -aa 1, = 5,6, 7, vrevee i shows that alternate members of the Pickering series (n, = 6, 8, 10, with members (n, = 3, 4,5, -.-) of the Balmer series, provided Rye = Ry. A careful examination by Paschen has shown that Balmer lines of H are not exactly coincident with Hoe Hp Hy He — (Fig. 8)won er alternate lines of the Pickering series of He", but are displaced by small intervals to ower wave numbers (longer wavelengths) as shown in Fig 8. This small displacement is to the difference in Ry and Ra which arises due to the finite mass (motion) of the nucleus ‘A careful observation shows that the series limits v. of Balmer and Pickering series differ by about 11 cm” '. Now For H: Won = * (y=) Balmer For He” : (Wedie’ = ae (ye). Pickering = 44cm Rye — Ru = 4[ ade (radu ] = 4 Mem” This result is in excellent agreement with the value obtained from theory. This is a good example to establish the truth of the effect of the motion of the nucleus. 10. Wilson-Sommerfeld Quantisation Rules Planck introduced his quantum theory by quantising the energy E of an atomic oscillator. According to Planck , an atomic oscillator can have only discrete energies which are multiples of hv’ (E = n hv’), where v’ is the frequency of the oscillator. Bohr, on the other hand, quantised the angular momentum of the electron moving in a circular orbit Wilson and Sommerfeld, in 1916, enunciated a set of rules for the quantisation of any physical system for which the coordinates are periodic functions of time. These are called “Wilson-Sommerfeld quantisation rules’, and include both the Planck and the Bohr quantisation as special cases, These rules can be stated as follows : For any physical system in which the coordinates are periodic functions of time, there exists a quantum condition for each coordinate. These quantum conditions are $ nda, = mh i) where q, is one of the coordinates, p, is the momentum associated with that coordinate, and n; is a quantum number taking integral values. te g reas that the integration is taken over a complete period of the coordinate q,. The integral is called the * . * s the ‘phase integral’ for the quantum number 1”, - Derivation of Planck's Quantisati quantum conditions to a one-dimen on of Energy : Let us apply Wilson-Sommerfeld kinetic) energy in terms of see na! simple harmonic oscillator. Its total (potential * Position x and linear momentum P, is E=U+K * = akg le kel meap. =] ym 7 iH + pe The relation between x 2B” 2mE = | and p, is 5 " «He equation ofan ellipse with semiaxes a and b giver On NREE and b= mE,Bohr-Sommerfeld Theory of Hydrogen Atom 21 pesado es Any instantaneous state of motion of the oscillator is represented by some point PR on the ellipse, plotted on a two-dimensional space having coordinates xandp,, as shown in Fig. 9. This plot is known as ‘phase space diagram’ of the oscillator. During ‘one cycle of oscillation, the point ie (x, p,) travels once around the ellipse, so that the value of the integral $ Prd is just equal to the area of the ellipse (Fig. 9) (nab). Thatis, § prdx = mab. Putting the above values of a and b, and solving we get 2nE fre BE IF v" be the frequency of oscillation, then v" = 5! Mk7m . Thus § prac = 5. According to the Wilson-Sommerfeld quantisation rule, expressed by eq. (i), we have iF $ reac = nh, nisan integer. Comparing the last two expressions, Een Vv or E=nhv', which is Planck's quantisation law. The allowed energy states of the oscillator can be tepresented by a series of ellipses in phase space, the area enclosed ~—bet ween Successive ellipses always being A, as shown in Fig. 10. (Fig. 10)_ E Atomic and Molecular Spectra Let us ¢ Momentum tive 2 tisation of Anew ilson-Sommerfeld rule. The pos is Quer from the ified in terms of plane . of Bohr’s entum ft specifi , Dita o0 of angular ei orbit Seems The momentum associate ig Bohr's qu ea cae leone a) wi - jated with the angular coorg; S dinates 8) w dr pile that associated tay ie I coordinate r isp, =" gr” ia the radial 2 sch is constant. For a Ci amr awn rule to the angular coordina g a iy the Wilson-Sommerfeld the lar orbit, r is constant 50 tha, 6 isp, =! p, is zero. Hence, we apply The rule $e dg, = nh becomes in this case only. The r , dq, fnaann pian or 2npy=nh . = B4, ” oon 4 : > ‘The angular momentum of an electron is usually designated by L’, so that we may write the last expression as = > Le= , n a which is Bohr quantisation law. 11. de Broglie’s Interpretation of Bohr’s Quantisation Law According to de Broglie conception of matter waves, an electron of mass m moving with velocity & has associated with it a wave of waveleng: th given by Az mv where h is Planck's coy ible ant: This wave-character of electron can account for the limited number of permissible orbits in an atone and also enables us to deduce the quantistd angular momentum Of an electron 1M an atom. We know that accordin, i 18 to Bohr, an electr; atom revolves in circular ace Ron-radiating orbi the nucleus, Let us fit this idea with tase Orbits around (Fig. 11)Bohr-Sommerfeld Theory of Hydrogen Atom 2 that only those orbits are Permitted for which the radius r is given by oh _ dmr=nh, n= 1,2,3,.. xu this were not so, then the waves in each travel around the orbit will not be in phase, and ina large number of travels the waves would interfere with each other in such a way that their average intensity would be zero. This would mean that an electron cannot be found in such an orbit. Hence, the last expression is a necessary condition for the electron to exist in it. Substituting 2 = h/m in the last expression, we get nr = 2h mv or =k, 2nmv Hence the magnitude of the angular momentum of the electron in its orbit must be ; : L= 2. mor n This is Bohr’s quantisation law. 12, Bohr’s Correspondence Principle According to the classical theory, an oscillating charged system would emit radiation of a particular frequency, namely, the frequency of the oscillator itself. According to quantum theory, however, radiation is emitted as a result of the system making a transition from a quantum state n; to another quantum state ny, and the frequency of radiation is determined by the difference in energy between the two states : ,_B-& va Bohr, in 1923, enunciated a principle which established a correspondence between the classical frequency and the quantum frequency. This principle consists of two parts : (i) The predictions of the quantum theory for the behaviour of any physical system must correspond to the predictions of the classical theory in the limit in which the quantum numbers specifying the state of the system become very large. ° (ii) Any selection rules which are necessary to obtain the required correspondence in the limit of large quantum numbers also hold for small quantum numbers. Let us apply this principle to the hydrogen atom. Let v be the velocity of electron (mass m, charge e) revolving in a Bohr orbit of radius r of the hydrogen atom. The condition of mechanical stability of the electron is me ied r 4nepP ‘The quantum condition is mors 24, aw lsu. Qn ‘These two equations give 5 é 0 Tnhe Whe and re nme’| 24 i Jectron in the orb i ncy of revolution of the ¢! The clasical frequency ofrevoluton of _2 J = Grcumference of orbit ~ 2mr me Beg hic Now, = R.., the Rydberg constant for infinitely heavy nucleus. = Ce i) = 3 This is the frequency which must be radiated by the moving electron classically. Now, the frequency radiated on the basis of quantum theory, when the electron drops from an initial orbit 1; to a final orbit ny, is given by yeh me (tl 1). Th Bed wl ne on) Again, introducing R.., we have 1 V=Roc 4 — ny This may be written in the following form : i i +N, V = Rc MME + mp np nj Let us consider the transition An=nj-ny=1, and write m=n and nm = my + 1 =n + 1. Then, the radiated quantum frequency is Ve Reeth, w(n + 1) When n is very large, we can write fetl . tn 2 Pista) oe Under this condition, the emitted quantum frequency is v = 2Ree, 3 vali) Equations (i) and (ii) yield Vee {f'we consider transitions An= 2,3, 4, we shall have radiation is identical with the lasicalfrequ copmantumtheory frequency v" of th ‘Ncy of the revolution (or its harmonics) of the accordance with Bohr’s Correspondence principle. 13. Sommertela’s Extension of Bohr's Model In Bobr's mode reatiction vs en } the electron could move only in circular orbits | ¥ arbitrary. Moreover, ‘spite of the striking numerical aeBohr Sommerfeld Theory of Hydrogen Atom 25 —_—————— rrr Am agreements, the Bohr's model could not explain the “fine structure’ of the hydrogen Spectral lines. The fine structure is splitting of the spectral lines into several close, distinct components when observed under equipment of high resolution, This means that each Bobr's energy level in hydrogen atom actually consists of several components which are close together in energy. Sommerfeld, in 1916, in an attempt to explain the fine structure, extended Bobr's model by assuming that the electron could move in elliptic orbits also, in addition to Bohr's circular orbits. He evaluated the size and shape of the allowed elliptic orbits, as well as the total energy of an electron moving in such an orbit, Let us consider the motion of an electron (mass m, charge ~ ¢) in an elliptic orbit, with nucleus (charge + Ze) at one focus (Fig. 12) The instantaneous position of the electron NUCLEUS can be described in terms of the plane polar coordinates rand @, which, being periodic functions of time, must be quantised separately. If p, and p, be the radial and the angular momenta of the electron, then according to Wilson-Sommerfeld quantisation rules, we have § re sah cai) a and J, pydd = kh, wait) where n,andk are integers, called ‘radial’ and ‘azimuthal’ quantum numbers respectively. ‘The second integral is easily evaluated because according to classical mechanics, the angular momentum p, of any isolated system is constant, Thus, rn [mtn = Hh “city or Qn” oo (tt This restriction on the orbital angular momentum is the same as in Bohr circular orbit theory. To evaluate the first integral, let us write oe ime (iv) and pye=mrd, Ay) where rand r6 are the radial and the angular components of the velocity of the electron.26 Atomic and Molecular Spectra : Laser Now, the polar equation of the ellipse is 1 _1 1 -ecos8 wfvi) ra qe . where VI-e = 2 catio of ‘semi-minor to semi-major axis), a Taking logarithmic differentiation of r with fespect to 8, we get | 1dr _ 1 esin@ \ Fea 1-e | ‘, - | mt 7 oro (rom eg. (vy : LarY esi’ a “ be 48) “(1 = ecos ey “a Now, p, = mr = nf = nie = meg. Using eq. (v), we have di P= a + o(viii) Also, dr = Lag. , 0 Using eq. (vii), we have 2 os P,dr = py e'sin’@ do Hence the integral in eq, (i) becomes an a nf © sin? 9.40 = nh. 0 (l~ecosey back A 1 The value of this definite inte; ralis 27 = 2s merle) 1 an - = nce 1}=ma h r But p, = £ bya (ii), ‘ alts = =a or Fron - et lee I n n> or 7: : Wort gts — or Wire 2 tL 5 +k Buvi—-e& = a’ *Propenty of ellipse.y Bohr-Sommerfeld Theory of Hydrogen Atom 2 BohrsSommerfeld Theory of HydrogenAtom = 1 ok. oa iX) aoiont+k Since n, and k are integers, we may put n+k=n, where 1 is called ‘principal’ or ‘total’ quantum number. In order to exclude “pendulum” orbits passing through the nucleus, Sommerfeld Postulated that the azimuthal quantum number k # 0", that is, k= 1,23, The radial quantum number n,, however, takes the zero value for which the orbit is circular. That is M = 0,1,2,3,...... ‘Therefore, n can take on the values : We 1LD Bay cceces Fora given value of n, the k can assume only the values KEWY3, ne The €q. (ix) now becomes This is the quantum condition for the elliptic orbits. Out of all the classical Possible ellipses, the electron can move only in those orbits for which the ratio of the minor to the major axis is the ratio of two integers, This quantises the size and the shape of the allowed elliptic orbits, Total Energy of Electron in allowed Orbit : Let us now calculate the total energy E of an electron in a quantised elliptic orbit. The energy is the sum of the kinetic energy K and the potential energy U. That is E=K+U 2 = dmc? + 76) - Te Using eq, (iv) and (v), we have 2 2 Llp? 4 Pol — 1 Ze exh 7+ | ther Again, using eq, (viii), we have pee [(ldry , \)__1 ze 2mPl\rde 4ne& r ter 2mEr mZer or -= |= -1l+ c vei) (ras Pe 2neopy Now, from eq, (vi), we have 2, 1 ecosg = SU = 8) “ik = 0, then b = 0 from eq. (ix), and the ellipse would beco: ‘Straight Ii through focus (nucieus). me me "Atomic and Molecular Spectra Lay, 28 ny 2 cos? ag €) or €’ cos 8 =) 1 - r 2 aoe? or e sin’? @ = & — €? cos’ 8 at -[r- Hs r ta - et , i 2 2 Puts A |- and Sisal, 2a) 5 r oo 8 ors (I = &cos 6y “Fae ~ at 2, al =e) a(l ~ e) Substituting this in eq. (vii), we have Dede i i ar. rd a (1 -e’) a(1 - e) ‘This is identical with eq. (xi). Hence, we can compare the coefficients of 2 and these two equations. Then, we have . 2mE i 1 pe al ~ mZe _ 2 and ; 2nepe all ~ e) 2 But 1 ~ e* = ©. therefore, the last two eq, become a 2mE -_l Pe g ti) and amZe 2a 2rap bP Ay Dividing eq. (xii) by the square of eq. (xiii), we have Bre Epe e er mZ e*(b?/a?) 32m pe or E=- kh aH Butp, = 2n OY eq. (iii), and 2 = f by eq. (x), xiv ap ee ee oe Same as for the Bohr's circular orbit, ‘That is tt Sul depends only on th . independent of the azimuthal quantum nite i Principal quantum number a, andsBohr-Sommerfeld Theory of Hydrogen Atom Size and Shape of Sommerfeld’s Elliptic Orbits : From eq. (xiii), we have mZee Aner Applying py = i, and 2. £ so that b = ak we have nmZe a ae wh’ & 242 or a= Ae. =(xv) nmZe we Now, ss = do (say), the radius of the smallest Bohr orbit of hydrogen atom. Hence, me we may write soolvi) Further, using b = ak, we have = Akay, «Xxvii) Eq. (xvi) and (xvii) determine the size and shape of Sommerfeld’s elliptic orbits. Now, the theory predicts that for a given value of n(= k + n,),& can take n possible different values (k = 1, 2, 3, ....). This means that for a given n, there are n orbits of different eccentricities (according to the condition at E which can be occupied by the electron. Let us consider the first few cases of hydrogen atom (Z = 1). For n = 1; wehavek = 1, so that from eq. (xvi) and eq. (xvii), we have = a 3 b= a. oa is a circular orbit of radius a> (Fig. 13). which is exactly the same =} as ioe ’ em hove (Fig. 13) (@) k=2sotha § ad iy) k= 1 sot 97 7e i) Thus, for n = 2, we have a Bohr's circular orbit of radius ert 4d, and an elliptic orbit with semi-major axis 4 a9 and semi-minor axis 2d (Fig. 14).Forn = 3, there are three types of poss! ‘Atomic and Molecular Spectra : Laser ible orbi one is the Bohr’s circular orbit of radius 9 ap , the d semi-minor axis 6 do, and the third axis 3a (Fig. 15). a = 9a Giiyk = 1 sothat , _ 34, Thus, out of the three possible orbits, one | second is an elliptic orbit of semi-major axis 9 ao and semi is an elliptic orbit with semi-major axis 9 dg and semi-minor g53 (Fig. 15) We see that corresponding to each value of the principal quantum number 1, there are n different allowed orbits. One of these is circular, just the orbit described by the original Bohr theory. The others are elliptic, all having the same semi-major axis as the radius of the circular orbit, but different semi-minor axes, The orbit having the lowest k is most elliptic. But, despite the very different paths followed by the electron moving in differen possible orbits for a given n, the total energy of the electron is the same. This means thal Sommerfeld’s introduction of elliptic orbits adds no new energy levels, and hence fail to explain the fine structure. The several orbits characterised by a common value of energ} are said to be ‘degenerate’, ‘To designate an orbit of given n and k values, the value of nis followed by one 0 the letters s,p.d.f.g,...... according as k = J, 2,3, 4,5 respectively. Fo example, the state m= 3,4 = 1 is writen as 35; and that n = 3, = 20s 3p. Iti Seen that the s-electron orbit (lowest k) is most elliptical in any family of orbits havin same major axis (same n), 14, Sommerteld’s Relativistic Correction Sommerfeld removed the de; different k-orbits for a given vn Beneracy in the total energy of the electron movin6 | by introducing the relativistic variation of mass of U electron. For an electron in the innermost orbit of the hydrogen atom, © = 10°?, or le ¢Bohr-Sommerfeld Theory of Hydrogen Atom 31 Although, this would give a relativistic correction to the total energy only of the order of 10°*, but itis just the order of the splitting of enery levels required to explain the observed fine structure of hydrogen spectral lines, In an elliptic orbit, the velocity of electron varies and is largest near the perihelion. ‘The actual size of the relativistic correction depends upon the average velocity of the electron which, in turn, depends on the ellipticity of the orbit, This means that the correction is different for different k-orbits of a given n, and thus the degeneracy is removed. Using the relativistic expression for the kinetic energy of the electron, 2 1 K = me (aoe oF 1), where mo is the rest mass of the electron, Sommerfeld obtained the following equation for the path of the electron : = = + Li ccos(y6) a ~ 1-¢ 1 r where y(<1) is a constant. This shows that r does not return to a given value when @ increases by 2m, but only when it increases by 2 /y which is greater than 2 x. Thus, the orbit of the electron is not a uniform rotating ellipse, but the perihelion of the orbit precesses in the same direction as the revolution of the electron. The advance of the perihelion perrevolution is 2% — 2x, as shown in Fig. 16. ee Y a0 on (Fig. 16) Taking the effect of relativistic precession into account, Sommerfeld calculated the total energy of an electron in an orbit characterised by the quantum numbers n and k as my Ze! Bay 3 Emi 7 alt = (|e o ap | Beant h n ({k 4n 2 where the quantity a(- )s @ pure number called ‘fine-structure cunstant’. Its 2ehc value is about iW . (@tis equal to the ratio of the velocity of electron in the first Bohr orbit of hydrogen to the velocity of light ¢ in vacuum). ‘The last expression may also be written as a= StAe 14 Ze ] ; +(e > aa)h ae is the Rydberg constant for an infinitely heavy nucleus. The term ehrc values of the hydrogen-Iike atom are therefore E eFhi+ te oy ie (i - 35 n32 Atomic and Molecular Spectra : Lase, LE ey, rote REEL. 2) * ~ an ‘The first term of this equation is the same as that derived by Bohr for circular orbits, and gives the major part of the energy. The second term is the relativity correction AT, such that 884-2) Now, Ria? = (1.097 x waa] 1 = $84 x 10'm'! = $84cm"!. 2 ars suZ(t - a} \ which is positive since k —v Fine-structure of Ho-line as predicted by Sommerfeld Theory (Fig. 17) Let us compare this result with experiment. Hansan obtained by experiment a photometric curve for the Ha-line of hydrogen. An analysis of this curve indicated the presence of five components, two strong and three weaker ones (Fig. 18). The spacing between the two main components was found to be 0:3297 cm”! which was in excellent agreement with Sommerfeld’s theory. There were however, two serious disagreements : (i) Experimentally, a rather strong component was observed on the small wave-number side of the main component II b. Calculation showed that this corresponds exactly to the transition n = 3, k = 1 > 1 = 2, k = | (IIb), which is forbidden by the selection rule and hence not given by theory. (ii) Experimentally, the component II b was stronger than the component I a, while reverse was the case in theory. These discrepancies were removed by introducing the spin of the electron and adopting the quantum: .nechanical relativistic correction. We shall return to the discussion of the hydrogen fine structure in a subsequent chapter.Atomic and Molecular Spectra : Lase, HANSAN’S EXPERIMENTAL ‘CURVE ib Ta mb Note : From quantum mechanical considerations, the azimuthal quantum number k of Bohr-Sommerfeld theory has been replaced by / + 1, where { is a new quantum number, having possible values : (= 0,1,2,3,....40(0 — I). 15. Shortcomings of Bohr-Sommerfeld Theory The Bohr-Sommerfeld theory was quite successful in explaining many experimental observations on the structure of atoms and simple spectra. Yet, it was not free from shortcomings. {i) Although the theory told how to calculate the energies of the allowed states of at atom, and the frequency of radiation emitted or absorbed in transitions between allowed states; but it could not tell how to calculate the rate at which such transitions take place. As such, it could not explain the variation in intensity of the spectral lines. (ii) The theory is applicable only to one-electron atoms like hydrogen, hydroget isotopes, singly-ionised helium, etc. It fails when applied to the neutral helium atom which has only two electrons. (iii) As we have seen, even in hydrogen-like atoms the theory become silent 0” the observed fine-structure of spectral lines. (iv) No logical reason was given for the introduction of quantum numbers. quantum numbers were introduced by Bohr as a postulate and adhoc selection rules W°"* adopted to explain the observed lines, Theys ee 38 Bohr-Sommerfeld Theory of Hydrogen Atom 35 oT sss (+) The theory did not throw any light on the distribution and arrangement of electrons in atoms, (vi) The success of the theory in dealing with the effect of a magnetic field on spectral lines was only partial. Tt could not explain anomalous Zeeman effect. These difficulties could not be resolved by further changes in Bohr'r theory. It became ‘apparent that the difficulties of the theory were caused by the failure of the atomic model then used. The solution to the problem came in 1925 and onwards in the form of quantum mechanics which yields all the correct results of the Bob's theory, such as stationary states with the correct energy values, explanation of emission and absorption of radiation in terms of transitions between stationary states, the Ritz combination principle, etc. In quantum mechanics, the quantum numbers appear automatically in the mathematical Solutions of the problems. The necessary selection rules also turn out to be a direct result of the mathematical treatment, Nevertheless, the so-called old quantum theory is still used as it is possible to go quite a long way with the Bohr’s model without coming into disagreement with many experimental observations, without going through complicated and lengthy mathematics used in quantum mechanics. SOLVED PROBLEMS 1, Calculate the speed of electron in the ath orbit of hydrogen atom. If relativistic correction is important for o/c > 0-005, find for which orbit this correction is necessary. Given : ¢ = 160 x 10"C, h = 663 x 10Js, ¢ = 30 x 10'ms'andey = 885 x 10°" C/N’. Solution. Let v be the velocity of electron (mass m, charge e) revolving in a Bohr orbit of hydrogen atom (Z = 1) of radius r. The condition of mechanical stability of the electron is mi lie @ r” 4ne 2° ” ‘The quantum condition is nh rr mor=ooe n= 1,2,3,... vei) Dividing eq. (i) by eq. (ii), we get 2 é = 2nhe Substituting the given values : 1.60 x 10° pe 2n (6-63 x 103s) (885 x 10°? C/N?) i i (2:18 x 10) ms"! This is the required value. Now 2.18 x 10° _ 0.0073 30x108 on Thus, form = 1, 2,3,... we have 2 = 0.0073, 0.0036, 0.0024, .. Hence the relativistic correction is necessary for n = 1 orbit only,%6 Atomic and Molecular Spectra ; " ifbvamgniinannuncbasctean 2. How many revolutions does an electron in the 1 = 2 state of a hydrogen atom make before dropping to the n = 1 state ? The average lifetime of an excited state 10"* second. (Ru = 1.097 x 10’ m') _ Solution. Let y bbe the velocity of electron (mass m, charge ¢) revolving in a Bohr Orbit of hydrogen atom (Z = 1) of radius 7, ‘The condition of mechanical stability of the electron is ‘The quantum conditions is i n=1,2,3,.. : é neg These two equation give eee and r= ‘The number of revolutions of the electron in the orbit v awe me _(2¢ = R(2£ ter awe teh e( | (#} For the n = 2 state, the frequency of revolution is Rac to Svbsttating the given valu of Rand the known vale of c, we get 1.097 x 10” m") 30 x 10's"! fa 4 me” Per second is = 82x 10g! Hence the oumber of revolutions ofthe electron ints life-ime of 10" second is = (82 « 105") x 108s 82 x 108 3. The series limit 3646 A. Calculate a7 M( 5-5} na 345, For the series limit wavelength, n = = ‘Thus, bo) 4 . ae] te 3606 x 10m 1097 10" my! A. Calculate the wavelength of the sight line ofthe Balmer series of hydrops atom. Given: R. = 109737 x 107m", Sobution. The wavelengths of the tines of Balmer Series are given by 1 4.4.5, 6,7, 8,9, 10, For the 8 th line, a = 10,Bohr-Sommerfeld Theory of Hydrogen Atom 37 Doe eee eee bd, ge fit . 4) Set oo Ra( 3 e) 25 25 or A= oR Gi) Now, the Rydberg constant for hydrogen is Ru = Re . re Mn where R., is Rydberg constant for infinitely heavy nucleus, m is the mass of electron, ‘and My is the mass of hydrogen nucleus (that is, proton). ‘We know that m/My, is 1/1836. 7 om | 8 Ry Tg 103677 x 101 Hence, from eq. (i) we have .=—_—_3 __, 6 x (109677 x 10° m™) = 3.799 x 107m = 37994. 5, The wavelength ef the first line of the Lyman series of hydrogen is qs A. Calculate the wavelength of the second line of the series, and the series limit. Solution. The wavelengths of the lines ‘of the Lyman series of hydrogen atom are given by 1 1 1 x? ed - ze BAA For the first line (A = i215 A), n = 2. 5 gel aR * TaeA a 4 * Rn = 5 (USA) For the second line (A = ?)." = Be Eten) = eu "5 gw RUDE A AO 215 9. 10254. For the series limit, n = ©. . pw fp = SHUTS. ound HH 6. (i) How much energy is required to remove an electron from a hydrogen atom in the ground state, and also in a state with 2 =8 ? (li) Calculate the corresponding energies of the singly-ionised helium atom. (m = 9:11 x 107" kg, ¢ = 1:60 x 10°” C, f= 663% 10" Js , 9 = 88S x 10"? C/N m’ and 1 eV 1:60 10°? J). orVv u Atomic and Molecular Specta Late Sobution, (1) The fequired to remove an electron from the hydrogen atom in th breed vn (1) aly (he he ry a) maven pa Peat? of the electron in the m= 1 orbit. Now, the energy of the electron in n th orbit hydrogen (Z = 1) is given by ne. als aah,23, eo sa(2} For the ground orbit, nel, Be Me tx 10) xox 10) tee x10 Fea s-2ITx1y 27x10) Tn Are © - 136 ev. lox iv ~~ 36° n= | orbit to infinity is 13-6 eV, This is known as the binding energy ofthe hydrogen atom. & 0 = eH oy ence he enerzy required o remove leon trom eit to nay in 213 ey (H) The energy expression for He* (Z = Dis ™ me (i (Baa yin a ee co sere rH me capone rH. Than, trea - 4K 106 © S44 ev and 440213 © O88 ev, 7, The wavelength of the first line of Bulmer serles Cateutate ( the lanisation potential, and (i) the fine Nrdrmgen staan th = 649 « 10 ™ 3406305 10 my ang VeVet Genie"), Staci. OD The wevtargtn othe Daler ies ae given by teal} 3] aedas « = eee vals) al ‘ Seasenig Fe * rete mw of hydrogen 68628 4. relation potential of theBohr-Sommerfeld Theory of Hydrogen Atom 39 ‘The ionisation potential of an atom is numerically equal to the (ionisation) energy required to remove an electron completely from the atom in the ground state. In hydrogen atom; the electron stays in the first orbit (n = 1). Hence the energy required to remove this electron to infinity (where the energy is considered to be zero) is numerically equal to the energy of the electron in the first orbit, We know that electron energy in the 1 th orbit of hydrogen atom is given by ‘ ea (4), n= 1,23. . ror Rhe me «Rete, Re nt | a | Ignoring the effect of finite nuclear mass, we can take Ry = Ra rn For the ground orbit, n = 1. » Ep =-Ryhe = = (1-097 x 107m) (6-63 x 10°75) 30 x 10's”) 218 x 10°77 f 19 ~ 2B x10 D2 - 136ev. 160 x 10°" J/eV Hence the energy required to remove the electron from n = 1 orbit to infinity is 13-6 eV. Obviously, the ionisation potential of the hydrogen atom is 13-6 volt. (ii) The first excitation potential of the atom is the energy required to shift the electron from n= 1 ton =2 orbit, that is, E; ~ 2. Now, E, =- 136 eV and z= Aba -34ev. vs Ey ~ Ey = 136-3-4 = 102 eV. Hence the first excitation potential is 10-2 volt. 8. Calculate the ionisation potential of hydrogen atom, Given : h=663x10°* Js, ¢ = 160 x 10° C,m = 911 x 10° kg, and gy = 885 x 10°” CUN-m’, Solution. The ionisation potential refers to the binding energy of the hydrogen atom (the energy binding the electron to the nucleus), which is numerically equal to the energy of the lowest state corresponding to n = 1. This is, with Z = 1, ‘4 E=- ah B eq h Lx 107" kg) (1.60 x 107 c* 8 (885 x 10" C/Nent)? (6-63 x 10" Js)" 2-217 x10") = RTI _ 13 60v. 160 x 10° "5 /eV ‘The ionisation potential is 13-6 ¥.Atomic and Molecular Spectra : Lae, 40 hoton emitteg by id wavelength of a pl . 5. Find the ene Enec tanaiton from an excited state with m = 10 t the qarogen — oat the recail speed of the hydrogen atom in tne habe ven ; Ren tain 10° ar! b= 60x I0™Js, 6 = 30x 10'ms ana a= 1H ’ ™H = 167 x 1077 kg, _ tte n ee i tom (Z = 1) inastate n Biven by Solution, The energy of electron in fod “ 01 E,=- “a The energy of the photon emitted during an electron transition from n= 10 to » = lis 14 Ew ~ E ~Make(a~ ) r 8 mg hy (99 = (1-097 x 10? mo!) 6-63 x 10745) (3.0 x 10 ms (7a) = 216 x 107 9y 216 x 10°97 160 x 10° yey The Momentum of the Photon is » ps £_ Ux t = 7:20 x 10°" kg ms, © 30x 10'ms To find the Wavelength of the Photon, we see that the atom (n= 1). Hence the photon emitted belo, Spectral lines in this series are Biven by = 135ev. drops to the Btound state ngs to the Lyman Series, The Wavelengths of the For n= 10, we have . DRO a = 921 x 10% o 921A, Finally, after the emission of photon, the hydrogen atom recoils wi 7:20 x 1977 kg ms"! (Same as that of hydrogen atom of mass my (say) is va P20 x1 eg! ™ 167 x 10", state. The liberated tron, ted state, emitting a 466-4 And (li) the of ti riginal S17 10 mh og energy of the origi Ise = 30 x 10° ms",Bohr-Sommerfeld Theory of Hydrogen Atom 4l E,=- Ryhe n = - 0.097 x 10’ m7!) (6.63 x 10°" J5) (3.0 x 10°ms7') ” = 218 x 1075 or 218 x 107 13.6¢eV 160 x10? IeV ee The energy of electron in the first excited state (n = 2) is B= 136 eV = - 3-40eV. (2y Further, the energy of the emitted 466-A photon is he _ 663 x 103s) (3.0 x 10m s~') x 466 x 10°'m = 42.7 x 10°'°J = 26-7eVv, Hence, the total energy of the liberated electron is — 340 eV + 26-7eV = 23-3eV, (ii) The energy required to ionise hydrogen atom, that is, to remove the electron from the atom in the ground state (n = 1) to infinity (where the energy is zero) is numerically equal to the energy of the electron in the n = | state, that is, E, , which is Ra- a = - 136eV. The required energy of ionisation is then 13-6 eV. Hence, the energy of the original photon is the energy of ionisation plus the energy of the liberated electron, that is, 136 eV + 233eV = 369eV, 11. A beam of electrons bombards a sample of hydrogen. Through what minimum potential difference must the electrons have been accelerated if the first line of the Balmar series is to be emitted ? Explain how many possible spectral lines can be expected if the atom finally attains the normal state. Given 2 Ry = 1.097 x 10’m™',h = 663 x 104 Jsandc = 30 x 10°ms"), Solution. Normally the hydrogen atoms are in the ground state (n=1). The first Balmer line is emitted when the atom returns from n= 3 to n =2 state. Hence in order to emit this line the atom must be first raised to the n =3 state by electron bombardment. Therefore, the energy of the bombarding electrons must be equal to the difference of energy between n = | and n = 3 states (E, ~ Ey). The energy of hydrogen atom in the » th state is g, = — Behe, n “8 -ky = Say he Substituting the given values :4a Atomic and Molecular Spectra Laser By ~ B= $007 sol me (663 « 10°%I 4) GO x 10m 2194 x 10°75 _ le wy 1-60 x 10°17 I/eV = 1210. Hence the bombarding electrons must be accel If the atom finally attains the ground state, 30392341291) 12, Show that the ionisation poten atom. [ LeV = 160 * 10°" 4) Jerated by 12-1 volt. the possible number of spectral lines is tial of He” is four times the value for hydrogen jal of an atom corresponds to the energy of the atom in Solution. The ionisation potenti the ground state, For one-electron atom, the ground-state energy is (ignoring effect of finite nuclear mass) Ee - Rohe or E,« 2. For He” and H, we have Z = 2 and | respectively. , Fue hy a4, 4 times that of H. Hence the ionisation potential of He’ is 13. A positronium atom is a system consisting of a positron and an electron revolving about their common centre of mass, which lies half-way between them, Compare its jonisation energy and emission spectrum with those of the hydrogen (Meerut 98 sp. paper) atom (with infinitely heavy nucleus), Solution. The positron has the same mass mm a5 the electron and has equal but positive charge. The reduced mass of the electron-positron atom is therefore im) (mm He nem electron in hydrogen is very nearly m. = 5m while the reduced mass of ‘The Rydberg constant fer for positronium, Rp, i therefore half tht fo ce ith infinitely heavy nucleus). Thus hydrogen (w Rp = Re: ‘The energy states of the positronium atom would then be given by ep, «eh aw BEM. @ n an The corresponding expression for hydrogen atom (with infinitely heavy nucleus) ' RZ he @ Ede 2-2 (Eu) 2 Now, Z = | for positronium atom as well as for hydrogen atom. from eq. (i) and (ii) that the ionisation energy, which is numerically the lowest state (1 = 1), of positronium atom is half of that of hydrogen Hence, We conc equal to the energy atom.Bohr-Sommerfeld Theory of Hydrogen Atom 43 Serenata crmeryeieropen Atm ‘The wavelengths of the emitted spectral lines of positronium atom and hydrogen atom are given by 1 1 1 Bes - 3] ? nny 1 1 1 and a. Rel ma My (3 3] Tus Be ey, The wavelengths of positronium lines are double than those of hydrogen lines. 14. Ap meson (charge — e , mass = 207 m, where m is mass of electron) can be captured by a proton to form a hydrogen-like “mesic” (or muonic) atom. Calculate the radius of the first Bohr orbit, the binding energy, and the wavelength of the first line in the Lyman series for such an atom. The mass of the proton is 1836 times the mass of electron. The radius of first Bohr orbit and the binding energy of hydrogen are 0:53 A and 13-6 eV respectively. ..= 109737 em"', Solution. The reduced mass of the system is we 207 m) (1836 m) _ 186 me 207 m+ 1836 m . From Bohr theory, the radius of the first orbit (n = 1) of a hydrogen-like atom for Z= 1, is given by (taking finite mass of nucleus in consideration) * Hey We oll Hep 1 Rpe n(86mye 186) eme? | The quantity in the bracket is the first Bohr orbit of hydrogen atom which is 0:53 A Therefore x 053A = 285x107? A. net 186 ‘The binding energy of an atom is equal to the energy of the lowest state (n = 1). Now, from Bohr's theory, the ground-state energy of the hydrogen-like mesic atom with Z = 1 isgivenby ‘ ‘ he me E=- =~ 186 = = 186 136eV = ~ 2530 eV. teh Beak . Hence the binding energy is 2530 eV. The wavelengths of the Lyman lines are given by 1 1 1 z = Rul 33 - a}: n=2,3,4,.., where Ry is the Rydberg constant for the mesic atom, For the first line, n = 2, so that 4 As Ry ‘ ‘ Now, Ry = HE R= Beo'h Beh’Atomic and Molecular Spectra : Laser 44 Ru = oR = 186 Re Hence pect e te: TRy 3X 186 Ro Now, R.. = 109737 cm’! (given). is 4 = = 653 x 10 'cm = 653A. 3x 186 x 109737 cm Lyman series is in the X-ray region of the muonic atom spectrum. 15. Calculate the radius of the first Bohr orbit in M4ph (Z = 82) for a L-mesic atom. The masses of 1 meson and proton are 207 times and 1836 times respectively the mass of electron, Given : h= 663 x10 "Ss, ¢= 160 x 10% m = 94 x 107 kg and € = 885 x 1077 C?N“' mr. (Moons sp. paper 36 Solution. The reduced mass of -mesic atom (formed by @ pO meson and a proton) is (207 m) (1836 ™) _ 186m. 4 = 307m + 1836 m where mr is mass of electron. Now, from Bohr's theory, the radius of the first orbit (n = 1) of a hydrogen-like mesic atom taking finite mass of nucleus in consideration is n= Heo ' myze’ . Substituting the given values ; = 68 * 10-5)? (885 x 10°77“! wm) 3:14 (186 x 9-1 x 10°” kg) x 82 x (1-60 x 10° Cy = 349 x 10m. 16. A mixture of ordinary hydrogen and tritium (a hydrogen isotope whose nucleus is approximately three times more massive than ordinary hydrogen) is excited and its spectrum studied. Calculate the shift in wavelength for the H,, lines of the two kinds of hydrogen. (Given : R.. = 109737 cm” y Solution. The wavelengths of the Hg lines(n = 3 n = 2) of hydrogen (\H') and tritium (jH’) are given by wi) lll) 1 tori. -s and ie = r( z and Ry are Rydberg constants for hydrogen and tritium respec! (ii) from (i), we get where Ry tively (Z =! for both). Taking reciprocals and subtracting ¢q hy ode S(L-4 Ht T $ Ru Rr 1+ t+ 36) My Mr) om | 5 R R. 5Ra\ Mn MrBohr-Sommerfeld Theory of Hydrogen Atom 45 But Mr = 3 My (given). 1) 36m 2) tom Res 2 ig = Now, 109737 cm” ' and Ma = 1836 (we know). 24 ee Wn be (109737 em" ') x 1836 = 238 x 10°%cm = 238A. 17. Radiation from a helium ion He’ is nearly equal in wavelength to the H., line, first line of Balmer series, (a) Between what values of n does the transition in He” occur ? (b) Is the wavelength larger or smaller than that of H, line ? (c) Calculate the wavelength difference. Given : Ry = 109677 cm™' and Rye = 189722.cm '. Solution. (a) The wavelengths of the Balmer series of hydrogen (H), and those of the Pickering series of helium ion (He”) are given by a} n= 3,4,5,6,... oC) n and 7} a= 5,6,7,8,... .. (ii) n Eq. (ii) can be written as , - a) n= 5,6,7,8,... ...(iti) n A comparison of eq. (i) and (iii) shows that alternate lines of pickering series (n = 6,8, 10, ...) nearly coincide with lines of Balmer series (a = 3,4,5,...) ; nearly because Rye= Ry (not exactly). Thus, the transition in He* corresponding to transition for Hq line (n = 3-9 n = 2) in H occurs for the following values : n= 6,4. (b) Since Rye > Ry. we conclude that Aye < Ay. (c) The wavelengths of the first line (n = 3) of H_and that of He” (n = 6) are given # 5R Looks - 2) ent ig 7 Fal ¥) 36 1 1 4)_ 5Rue and ie 7 Be(32 Ge] Ge ; : = 36/1 _ fa = Bae = 3 (Re i | _ ft 5 | 109677em™' 109722 cm"! = 8001177 x 10"%em - 9.1139 x 10°F em) = # x 8 x 10%cm) = 27:36 x 10cm = 2-736 x 10°Scm = 2.7364.46 - QUESTIONS 10, 1. 12, 1. + Explain why lines of the Balmer series are not observed in absorption . Give postulates of Bohr’s theory and derive an expression for the Rydbe State Bohr’s postulates and deduce an expression for the allowed e; hydrogen atom. Show on an energy level diagram the observed tr: are the limitations of Bohr's theory ? Nergies of 1 fansitions, What » Using Bohr’s theory, calculate the radius of the first orbit of the electron Movin, ig around the proton, in terrestrigy Stars, taking inty Sources, but they have been observed in the absorption spectra of some Deduce the expression for the series Spectra of a hydrogen-like atom, account the finite mass of the nucleus. Constant. Explain why the value of this constant for helium is different than fe hydrogen. How has this difference been used to determine the ratios m / My a e/m, - Apply Bohr's model to singly-ionised helium, What relationship exists between this sepctrum and the hydrogen spectrum ? State and explain Wilson-Sommerfeld quantisation rules. Use them to deduce Planck's energy quantisation law, and Bohr’s angular momentum quantisation law . How de Broglie’s concept of matter waves supports the quantisation of circular orbits of Bohr theory ? . Explain Bohr's correspondence principle. Prove that for very large quantum numbers, the quantum theory frequency and the classical orbit frequency become equal. Discuss analytically the Bohr-Sommerfeld theory of elliptical orbits of hydrogen atom and compare its results with those of Bohr’s theory of circular orbits, Discuss the characteristics of Sommerfeld’s elliptical orbits. Show that the $-electron orbit is most elliptic in any family of orbits having the same major axis, What is the meaning of degeneracy of elliptic orbits in Sommerfeld’s theory of elliptic orbits ? How is it removed by relativistic variation of electron mass ? How far does it help in explaining the fine structure of Hy line ? PROBLEMS (Use the following physical constants wherever required.) h = 663 x 10 “Js c= 30x 108ms! m = 91 x 107"'kg m, = 167 x 10 "kg (proton mass) m/ My = 1/1836 e = 160 x 10°C R. = 109737 cm! k= 138 x 107 9K! 19 1eV = 160 x 10° "J. is The angular momentum of the electron in a hydrogen-like _ tn 7.382 x 10° “Js. Find the quantum number of the energy level occuple Aus electron.— Bohr-Sonmerfeld Theory of Hydrogen Atom 47 2 3. 4, 10. 1. 12. 13. 14. A hydrogen atom in the ground state absorbed a 20-0-eV photon. What is the speed of the liberated electron ? The energy of electron in the ground state is ~ 13-6 eV. Ans. 1:5 x 10°ms"!, Find the wavelength of the photon emitted when a hydrogen atom goes from the n = 10 state to its ground state. ‘Ans. 920 A Calculate the wavelength of the transition from a level for which n = 7 toa level for which a = 6 for quadruply-ionised boron (B“**). The atomic number of boron is $ and its Rydberg constant is 1.0973 x 10° cm™!. Ans. 4946-4 A. The wavelength of the second member of Balmer series of hydrogen is 4861 A. Calculate the wavelength of the first member. Ans, 65623 A. At what temperature will the average molecular kinetic energy in gaseous hydrogen be equal to the binding energy of hydrogen atom ? Ans. 1-05 x 10°K. The wavelength of the second member of the Balmer series of hydrogen is 4861 A. Calculate the ionisation potential of hydrogen atom. Ans, 13-6 volt. A 12-1-eV photon is fully absorbed by a hydrogen atom in the ground state, and the atom is excited. What is the quantum number of the excited state ? The ground state (negative) energy of hydrogen atom is 13-6 eV. Ans. 3. An electron is inn = 3 level of hydrogen. Compute the energy required to ionise the atom. Ans. 1-51 eV. Calculate the energy required to remove the electron from singly-ionised helium. Ans. 54-4 eV. The spectroscopic values of Rydberg constant for hydrogen and ionised helium are 109677-7 cm”! and 109722:4 cm ' respectively. Calculate e/m of electron. The specific charge of hydrogen ion, e/Myz , is 96490 C/g. Ans. 1-77 x 10"! Crkg. Ina transition to a state of excitation energy 10-19 eV, an hydrogen-like atom emits a 4890-A photon. Find the binding energy of the initial state. (Meerut special paper 2003) Ans.— 7-66 eV. A mixture of ordinary hydrogen and deuterium (whose nucleus is about two times more massive than ordinary hydrogen) is excited and its spectrum observed. How far apart in wavelength will the Hq. lines of two kinds of hydrogen be ? Ans. 1:78 A. Determine the mass ratio of deuterium and hydrogen atoms if their Hg lines have wavelengths 6561-01 A and 6562-80 A respectively. Ans. 2:003 Quantum Mechanics of Hydrogen Atom : Angular Momentum and Parity ooOoOoOoo——————SE 00a 1. Limitations of Classical Mechanics Bohr model of the hydrogen atom accounts for the hydrogen line spectrum, a witha Humber of shortcomings. For example, it does not explain the fine a ah ° spect lines and the intensity variation in them. Moreover, its use is limited a 1c (one lectron) hydrogen and hydrogen-like atoms; it cannot explain the spectra o complex atoms, Finally, but most important, it does not tell how electrons interact with atoms, and atoms with atoms, to give the observed properties of matter. The cause of these shortcomings goes back to the limitations of the classical mechanics itself which is usually applied to explain the properties of systems. The classical mechanics is based on the assumption that in any system of particles it is Possible to measure precisely the quantities like position, velocity, momentum, acceleration, etc, which characterise the state of the system at any instant. The equations of motion then enable us to determine these quantities, and hence the state of the system, at all later instants. The assumption is valid in our everyday experience. This is why classical mechanics provides correct explanation for the behaviour of macroscopic systems. The assumption is, however, in conflict with the uncertainty principle which becomes important in the atomic domain, According to this Principle, the position and momentum of a particle cannot be accurately measured at the same time. The measurement of one quantity introduces an uncertainty into the other. Therefore, classical mechanics which assumes both to have definite values at all instants, is not valid for atomic systems. This is the reason that the Bohr model, which was Just a classical atomic model in which quantisation was introduced arbitrarily, failed to give a complete explanation of the behaviour of atomic systems, In fact, the success of classical mechanics in case of Macroscopic systems is due to the fact that such systems consist of so many individual atoms that departures from average behaviour are unnoticeable. But, truely speaking, placed by a theory of greater generality. Quantum mechanics, developed by Schroedinger, is a correct. replacement. Me_— Quantum Mechanics of Hydrogen Atom : Angular Momentum and Parity 49 oO W=Vinyn0 Vis édlled the “wave function” as it characteristies the (de Broglie) waves associated with the moving particle. It is postulated that Y has the from of a solution of the classical wave equation. ‘The differential equation representing a three-dimensional wave motion is ay ey ey _ say Ai) ae ay ae ar’ where v is the wave velocity. Now, the wavelength associated with a particle of mass m moving with velocity v is given by ae. mv Applying Einstein's postulate E = hv’ connecting the frequency v’ of the de Broglie waves with the total ensrgy E of the particle, we have 2 tl... ova? (EYh) (A/m vy? Making this substitution in eq. (i), we get ey ey Fy _ wr ey 2 toa ty ar” ay © ar ar FFL F) mol Fy o 3 wii) $b = * ar ae tat |¥" Ba The solution of this equation is of the form Da ye tnieu iii) where w is a function of space coordinates only (independent of time), that is, W=¥i%y2- Differentiating eq. (iii) with respect to time twice, we get ¥ = ye EM oni Eshy it 4m oni =— tye 2RiEWh / ey Substituting for W and re in eq. (ii), we get ey 7 # Rm? . S+5+5]/y-- ey. seali¥) ar * a? ae | we Y ; For non-relativistic motion of the particle, the particle's kinetic energy K = 1 mv”. Thus, if Vis the potential energy of the particle, then we can write pmol=K=E-V or my? = 2m(E-V). Making this substitution in eq. (iv), we get 2 2 2 a (Bde) tite- om ae” ay * ae B‘Atomic and Molecular Spectra : Laser so Let us use the symbol a % ,# Staty ax ay ae . Vis called ‘Laplacian operator’ or ‘del squared’ in rectangular coordinates. The last eq, is now written as v= This is Schroedinger's time-independent (steady-state) wave equation for a particle. Its (time-independeut) solutions w are called “eigenfunctions”. They determine the space dependence of the wave function W. 3. Physical Interpretation of Wave Function A satisfactory interpretation of the wave function W associated with a moving particle was given by Born in 1926. Born postulated that the square of the magnitude of the wave function, |G! (or 7 W*, if W is complex), evaluated at a particular point at any instant is proportional to the probability of finding the particle at that point. A large value of | JP means a large possibility of the panticle’s presence, while a small value of 17? means the slight possibility of its presence. | WF is called the ‘probability density’, and Wis the ‘probability amplitude’t. According to this interpretation, the probability of finding the particle within an element of volume dt is |W I? dt. Since the particle is certainly somewhere, the integral of 19? dt over the whole space must be unity, that is J Waren. A wave function that obeys this equation is said to be ‘normalised’. Every acceptable wave function must be normalisable. 4, Required Properties of Eigenfunctions To be an acceptable solution, an eigenfunction y must fullfil the following Tequirements : (i) y must be finite everywhere. If, for instance, y is infinite for a particular point, the same would be true for the wave function . It would mean an infinitely large Probability of finding the particle at that point. This would violate the uncertainty Principle. Therefore, y must have a finite, ot zero, value at any point. (ii) y must be single-valued, If y has more than one value at any point, it would mean more than one value of probability of finding the particle at that point which is obviously rediculous. t 's complex, with both real and imaginary parts, then the probability is given by the product of ¥ and its complex conjugate ¥ *. The complex conjugate WeN=T) by -1 reryuhere Reapears ithe Rnoton es fee ee coed yap YrAris v'=A-iB, somtyy ew PP ey Thus, 7 ¥* is abways a positive real q eri then