12.4 BOHR MODEL OF THE HYDROGEN ATOM The model of the atom proposed by Rutherford assumes that the atom, consisting of a central nucleus and revolving electron is stable much like sun-planet system which the model imitates. However, there are some fundamental differences between the two situations. While the planetary system is held by gravitationalforce, the nucleus-electron system being charged NIELS objects, interact by Coulomb’s Law of force. We know that an object which moves in a circle is being constantly accelerated – the acceleration being centripetal in nature. According to classical HENRIK electromagnetic theory, an accelerating charged particle emits radiation in the form of electromagnetic waves. The energy of an accelerating electron should therefore, Niels Henrik David Bohrcontinuously decrease. The electron would spiral (1885 – 1962) Danish DAVID inward and eventually fall into the nucleus (Fig. 12.6). physicist who explained the Thus, such an atom can not be stable. Further, spectrum of hydrogen atom according to the classical electromagnetic theory, the based on quantum ideas. BOHR He gave a theory of nuclearfrequency of the electromagnetic waves emitted by the fission based on the liquid- revolving electrons is equal to the frequency of drop model of nucleus. revolution. As the electrons spiral inwards, their angular Bohr contributed to the (1885 velocities and hence their frequencies would change clarification of conceptual – continuously, and so will the frequency of the light problems in quantum emitted. Thus, they would emit a continuous spectrum, mechanics, in particular by in contradiction to the line spectrum actually observed. proposing the comple- 1962) Clearly Rutherford model tells only a part of the story mentary principle. implying that the classical ideas are not sufficient to explain the atomic structure. 297 Reprint 2025-26 Physics FIGURE 12.6 An accelerated atomic electron must spiral into the nucleus as it loses energy. Example 12.4 According to the classical electromagnetic theory, calculate the initial frequency of the light emitted by the electron revolving around a proton in hydrogen atom. Solution From Example 12.3 we know that velocity of electron moving around a proton in hydrogen atom in an orbit of radius 5.3 × 10–11 m is 2.2 × 10–6 m/s. Thus, the frequency of the electron moving around the proton is v 2.2 × 10 6 m s −1 ν = = −11 2 π r 2 π 5.3 × 10 m ( ) 12.4 » 6.6 × 1015 Hz. According to the classical electromagnetic theory we know that the frequency of the electromagnetic waves emitted by the revolving electrons is equal to the frequency of its revolution around the nucleus. EXAMPLE Thus the initial frequency of the light emitted is 6.6 × 1015 Hz. It was Niels Bohr (1885 – 1962) who made certain modifications in this model by adding the ideas of the newly developing quantum hypothesis. Niels Bohr studied in Rutherford’s laboratory for several months in 1912 and he was convinced about the validity of Rutherford nuclear model. Faced with the dilemma as discussed above, Bohr, in 1913, concluded that in spite of the success of electromagnetic theory in explaining large-scale phenomena, it could not be applied to the processes at the atomic scale. It became clear that a fairly radical departure from the established principles of classical mechanics and electromagnetism would be needed to understand the structure of atoms and the relation of atomic structure to atomic spectra. Bohr combined classical and early quantum concepts and gave his theory in the form of three postulates. These are : (i) Bohr’s first postulate was that an electron in an atom could revolve in certain stable orbits without the emission of radiant energy, contrary to the predictions of electromagnetic theory. According to 298 this postulate, each atom has certain definite stable states in which it Reprint 2025-26 Atoms can exist, and each possible state has definite total energy. These are called the stationary states of the atom. (ii) Bohr’s second postulate defines these stable orbits. This postulate states that the electron revolves around the nucleus only in those orbits for which the angular momentum is some integral multiple of h/2π where h is the Planck’s constant (= 6.6 × 10–34 J s). Thus the angular momentum (L) of the orbiting electron is quantised. That is L = nh/2π (12.5) (iii) Bohr’s third postulate incorporated into atomic theory the early quantum concepts that had been developed by Planck and Einstein. It states that an electron might make a transition from one of its specified non-radiating orbits to another of lower energy. When it does so, a photon is emitted having energy equal to the energy difference between the initial and final states. The frequency of the emitted photon is then given by hν = Ei – Ef (12.6) where Ei and Ef are the energies of the initial and final states and Ei > Ef. For a hydrogen atom, Eq. (12.4) gives the expression to determine the energies of different energy states. But then this equation requires the radius r of the electron orbit. To calculate r, Bohr’s second postulate about the angular momentum of the electron–the quantisation condition – is used. The radius of nth possible orbit thus found is  n 2   h  2 4 πε0 rn =    2 (12.7)  m   2 π  e The total energy of the electron in the stationary states of the hydrogen atom can be obtained by substituting the value of orbital radius in Eq. (12.4) as  e 2   m  2 π  2  e 2  E n = −   2      8 πε0   n  h   4 πε0  me 4 or E n = − 2 2 2 (12.8) 8n ε0 h Substituting values, Eq. (12.8) yields −18 2.18 × 10 E n = − 2 J (12.9) n Atomic energies are often expressed in electron volts (eV) rather than joules. Since 1 eV = 1.6 × 10–19 J, Eq. (12.9) can be rewritten as 13.6 E n = − 2 eV (12.10) n The negative sign of the total energy of an electron moving in an orbit means that the electron is bound with the nucleus. Energy will thus be required to remove the electron from the hydrogen atom to a distance 299 infinitely far away from its nucleus (or proton in hydrogen atom). Reprint 2025-26 Physics 12.4.1 Energy levels The energy of an atom is the least (largest negative value) when its electron is revolving in an orbit closest to the nucleus i.e., the one for which n = 1. For n = 2, 3, ... the absolute value of the energy E is smaller, hence the energy is progressively larger in the outer orbits. The lowest state of the atom, called the ground state, is that of the lowest energy, with the electron revolving in the orbit of smallest radius, the Bohr radius, a 0. The energy of this state (n = 1), E1 is –13.6 eV. Therefore, the minimum energy required to free the electron from the ground state of the hydrogen atom is 13.6 eV. It is called the ionisation energy of the hydrogen atom. This prediction of the Bohr’s model is in excellent agreement with the experimental value of ionisation energy. At room temperature, most of the hydrogen atoms are in ground state. When a hydrogen atom receives energy by processes such as electron collisions, the atom may acquire sufficient energy to raise the electron to higher energy states. The atom is then said to be in an excited state. From Eq. (12.10), for n = 2; the energy E2 is –3.40 eV. It means that the energy required to excite an electron in hydrogen atom to its first excited state, is an FIGURE 12.7 The energy level energy equal to E2 – E1 = –3.40 eV – (–13.6) eV = 10.2 eV. diagram for the hydrogen atom. Similarly, E3 = –1.51 eV and E3 – E1 = 12.09 eV, or to exciteThe electron in a hydrogen atom the hydrogen atom from its ground state (n = 1) to second at room temperature spends most of its time in the ground excited state (n = 3), 12.09 eV energy is required, and so state. To ionise a hydrogen on. From these excited states the electron can then fall back atom an electron from the to a state of lower energy, emitting a photon in the process. ground state, 13.6 eV of energy Thus, as the excitation of hydrogen atom increases (that is must be supplied. (The horizontal as n increases) the value of minimum energy required to lines specify the presence of free the electron from the excited atom decreases. allowed energy states.) The energy level diagram* for the stationary states of a hydrogen atom, computed from Eq. (12.10), is given in Fig. 12.7. The principal quantum number n labels the stationary states in the ascending order of energy. In this diagram, the highest energy state corresponds to n =¥ in Eq, (12.10) and has an energy of 0 eV. This is the energy of the atom when the electron is completely removed (r = ¥) from the nucleus and is at rest. Observe how the energies of the excited states come closer and closer together as n increases. 12.5 THE LINE SPECTRA OF THE HYDROGEN ATOM According to the third postulate of Bohr’s model, when an atom makes a transition from the higher energy state with quantum number ni to the lower energy state with quantum number nf (nf < ni), the difference of energy is carried away by a photon of frequency nif such that * An electron can have any total energy above E = 0 eV. In such situations the 300 electron is free. Thus there is a continuum of energy states above E = 0 eV, as shown in Fig. 12.7. Reprint 2025-26 Atoms hvif = Eni – Enf (12.11) Since both nf and ni are integers, this immediately shows that in transitions between different atomic levels, light is radiated in various discrete frequencies. The various lines in the atomic spectra are produced when electrons jump from higher energy state to a lower energy state and photons are emitted. These spectral lines are called emission lines. But when an atom absorbs a photon that has precisely the same energy needed by the electron in a lower energy state to make transitions to a higher energy state, the process is called absorption. Thus if photons with a continuous range of frequencies pass through a rarefied gas and then are analysed with a spectrometer, a series of dark spectral absorption lines appear in the continuous spectrum. The dark lines indicate the frequencies that have been absorbed by the atoms of the gas. The explanation of the hydrogen atom spectrum provided by Bohr’s model was a brilliant achievement, which greatly stimulated progress towards the modern quantum theory. In 1922, Bohr was awarded Nobel Prize in Physics.

12.6 DE BROGLIE’S EXPLANATION OF BOHR’S SECOND POSTULATE OF QUANTISATION Of all the postulates, Bohr made in his model of the atom, perhaps the most puzzling is his second postulate. It states that the angular momentum of the electron orbiting around the nucleus is quantised (that is, Ln = nh/2p; n = 1, 2, 3 …). Why should the angular momentum have only those values that are integral multiples of h/2p? The French physicist Louis de Broglie explained this puzzle in 1923, ten years after Bohr proposed his model. We studied, in Chapter 11, about the de Broglie’s hypothesis that material particles, such as electrons, also have a wave nature. C. J. Davisson and L. H. Germer later experimentally verified the wave nature of electrons in 1927. Louis de Broglie argued that the electron in its circular orbit, as proposed by Bohr, must be seen as a particle wave. In analogy to waves travelling on a string, particle waves too can lead to standing waves under resonant conditions. From FIGURE 12.8 A standing wave Chapter 14 of Class XI Physics textbook, we know that when is shown on a circular orbit a string is plucked, a vast number of wavelengths are excited. where four de Broglie wavelengths fit into theHowever only those wavelengths survive which have nodes circumference of the orbit. at the ends and form the standing wave in the string. It means that in a string, standing waves are formed when the total distance travelled by a wave down the string and back is one wavelength, two wavelengths, or any integral number of wavelengths. Waves with other wavelengths interfere with themselves upon reflection and their amplitudes quickly drop to zero. For an electron moving in nth circular orbit of radius rn, the total distance is the circumference of the orbit, 3012prn. Thus Reprint 2025-26 Physics 2p rn = nl, n = 1, 2, 3... (12.12) Figure 12.8 illustrates a standing particle wave on a circular orbit for n = 4, i.e., 2prn = 4l, where l is the de Broglie wavelength of the electron moving in nth orbit. From Chapter 11, we have l = h/p, where p is the magnitude of the electron’s momentum. If the speed of the electron is much less than the speed of light, the momentum is mvn. Thus, l = h/ mvn. From Eq. (12.12), we have 2p rn = n h/mvn or m vn rn = nh/2p This is the quantum condition proposed by Bohr for the angular momentum of the electron [Eq. (12.15)]. In Section 12.5, we saw that this equation is the basis of explaining the discrete orbits and energy levels in hydrogen atom. Thus de Broglie hypothesis provided an explanation for Bohr’s second postulate for the quantisation of angular momentum of the orbiting electron. The quantised electron orbits and energy states are due to the wave nature of the electron and only resonant standing waves can persist. Bohr’s model, involving classical trajectory picture (planet-like electron orbiting the nucleus), correctly predicts the gross features of the hydrogenic atoms*, in particular, the frequencies of the radiation emitted or selectively absorbed. This model however has many limitations. Some are: (i) The Bohr model is applicable to hydrogenic atoms. It cannot be extended even to mere two electron atoms such as helium. The analysis of atoms with more than one electron was attempted on the lines of Bohr’s model for hydrogenic atoms but did not meet with any success. Difficulty lies in the fact that each electron interacts not only with the positively charged nucleus but also with all other electrons. The formulation of Bohr model involves electrical force between positively charged nucleus and electron. It does not include the electrical forces between electrons which necessarily appear in multi-electron atoms. (ii) While the Bohr’s model correctly predicts the frequencies of the light emitted by hydrogenic atoms, the model is unable to explain the relative intensities of the frequencies in the spectrum. In emission spectrum of hydrogen, some of the visible frequencies have weak intensity, others strong. Why? Experimental observations depict that some transitions are more favoured than others. Bohr’s model is unable to account for the intensity variations. Bohr’s model presents an elegant picture of an atom and cannot be generalised to complex atoms. For complex atoms we have to use a new and radical theory based on Quantum Mechanics, which provides a more complete picture of the atomic structure. * Hydrogenic atoms are the atoms consisting of a nucleus with positive charge +Ze and a single electron, where Z is the proton number. Examples are hydrogen atom, singly ionised helium, doubly ionised lithium, and so forth. In these 302 atoms more complex electron-electron interactions are nonexistent. Reprint 2025-26 Atoms SUMMARY 1. Atom, as a whole, is electrically neutral and therefore contains equal amount of positive and negative charges. 2. In Thomson’s model, an atom is a spherical cloud of positive charges with electrons embedded in it. 3. In Rutherford’s model, most of the mass of the atom and all its positive charge are concentrated in a tiny nucleus (typically one by ten thousand the size of an atom), and the electrons revolve around it. 4. Rutherford nuclear model has two main difficulties in explaining the structure of atom: (a) It predicts that atoms are unstable because the accelerated electrons revolving around the nucleus must spiral into the nucleus. This contradicts the stability of matter. (b) It cannot explain the characteristic line spectra of atoms of different elements. 5. Atoms of most of the elements are stable and emit characteristic spectrum. The spectrum consists of a set of isolated parallel lines termed as line spectrum. It provides useful information about the atomic structure. 6. To explain the line spectra emitted by atoms, as well as the stability of atoms, Niel’s Bohr proposed a model for hydrogenic (single elctron) atoms. He introduced three postulates and laid the foundations of quantum mechanics: (a) In a hydrogen atom, an electron revolves in certain stable orbits (called stationary orbits) without the emission of radiant energy. (b) The stationary orbits are those for which the angular momentum is some integral multiple of h/2p. (Bohr’s quantisation condition.) That is L = nh/2p, where n is an integer called the principal quantum number. (c) The third postulate states that an electron might make a transition from one of its specified non-radiating orbits to another of lower energy. When it does so, a photon is emitted having energy equal to the energy difference between the initial and final states. The frequency (n) of the emitted photon is then given by hn = Ei – Ef An atom absorbs radiation of the same frequency the atom emits, in which case the electron is transferred to an orbit with a higher value of n. Ei + hn = Ef 7. As a result of the quantisation condition of angular momentum, the electron orbits the nucleus at only specific radii. For a hydrogen atom it is given by  n 2   h  2 4 πε0 rn = 2  m   2 π  e The total energy is also quantised: me 4 E n = − 2 2 2 8n ε0 h = –13.6 eV/n2 The n = 1 state is called ground state. In hydrogen atom the ground state energy is –13.6 eV. Higher values of n correspond to excited states (n > 1). Atoms are excited to these higher states by collisions with other atoms or electrons or by absorption of a photon of right frequency. 303 Reprint 2025-26 Physics 8. de Broglie’s hypothesis that electrons have a wavelength λ = h/mv gave an explanation for Bohr’s quantised orbits by bringing in the wave- particle duality. The orbits correspond to circular standing waves in which the circumference of the orbit equals a whole number of wavelengths. 9. Bohr’s model is applicable only to hydrogenic (single electron) atoms. It cannot be extended to even two electron atoms such as helium. This model is also unable to explain for the relative intensities of the frequencies emitted even by hydrogenic atoms. POINTSPOINTSPOINTSPOINTSPOINTS TOTOTOTOTO PONDERPONDERPONDERPONDERPONDER 1. Both the Thomson’s as well as the Rutherford’s models constitute an unstable system. Thomson’s model is unstable electrostatically, while Rutherford’s model is unstable because of electromagnetic radiation of orbiting electrons. 2. What made Bohr quantise angular momentum (second postulate) and not some other quantity? Note, h has dimensions of angular momentum, and for circular orbits, angular momentum is a very relevant quantity. The second postulate is then so natural! 3. The orbital picture in Bohr’s model of the hydrogen atom was inconsistent with the u quantum mechanics in which Bohr’s orbits are regions where the electron may be found with large probability. 4. Unlike the situation in the solar system, where planet-planet gravitational forces are very small as compared to the gravitational force of the sun on each planet (because the mass of the sun is so much greater than the mass of any of the planets), the electron-electron electric force interaction is comparable in magnitude to the electron- nucleus electrical force, because the charges and distances are of the same order of magnitude. This is the reason why the Bohr’s model with its planet-like electron is not applicable to many electron atoms. 5. Bohr laid the foundation of the quantum theory by postulating specific orbits in which electrons do not radiate. Bohr’s model include only one quantum number n. The new theory called quantum mechanics supports Bohr’s postulate. However in quantum mechanics (more generally accepted), a given energy level may not correspond to just one quantum state. For example, a state is characterised by four quantum numbers (n, l, m, and s), but for a pure Coulomb potential (as in hydrogen atom) the energy depends only on n. 6. In Bohr model, contrary to ordinary classical expectation, the frequency of revolution of an electron in its orbit is not connected to the frequency of spectral line. The later is the difference between two orbital energies divided by h. For transitions between large quantum numbers (n to n – 1, n very large), however, the two coincide as expected. 7. Bohr’s semiclassical model based on some aspects of classical physics and some aspects of modern physics also does not provide a true picture of the simplest hydrogenic atoms. The true picture is quantum mechanical affair which differs from Bohr model in a number of fundamental ways. But then if the Bohr model is not strictly correct, why do we bother about it? The reasons which make Bohr’s model still useful are: Reprint 2025-26 Atoms (i) The model is based on just three postulates but accounts for almost all the general features of the hydrogen spectrum. (ii) The model incorporates many of the concepts we have learnt in classical physics. (iii) The model demonstrates how a theoretical physicist occasionally must quite literally ignore certain problems of approach in hopes of being able to make some predictions. If the predictions of the theory or model agree with experiment, a theoretician then must somehow hope to explain away or rationalise the problems that were ignored along the way. EXERCISES

12.6 (a) Using the Bohr’s model calculate the speed of the electron in a hydrogen atom in the n = 1, 2, and 3 levels. (b) Calculate the orbital period in each of these levels.