12.5 A hydrogen atom initially in the ground level absorbs a photon, which excites it to the n = 4 level. Determine the wavelength and frequency of photon.

12.7 The radius of the innermost electron orbit of a hydrogen atom is 5.3×10–11 m. What are the radii of the n = 2 and n =3 orbits?

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