OBJECTIVES In this chapter, you will learn about, = experiments which proved the inadequacies of classical mechanics = Heisenberg uncertainty principle = significance of wave functions and quantum numbers = origin of the orbitals m= salient features of the Schrodinger equation which is central to the quantitative theories of bonding ing between different atoms or molecules and to In order to comprehend the nature of bondi quantum interpret the kinetics of chemical reactions from first principles, concepts involving chemistry are essential, Some illustrative examples in structural chemistry which involve the principles of quantum chemistry are estimation of electron distribution, construction of molecular orbitals and selection rules for spectroscopy 11 ADVENT OF QUANTUM CHEMISTRY The development of quantum chemical concepts is attributed to the pioneering work o' Bohr, Max Planck, Max Born, de Broglie, Heisenberg, Schrodinger and Albert Einstein, efficacy of quantum mechanics is usually ascribed to the inability of classical (Newtonian) mechanics in interpreting the experiments pertaining to (i) black body radiation (ji) the photoelectric effect and (iii) the Zeeman effect. The 1.2 BOHR MODEL The Rutherford model of the atom assumed that the electrons move around the nucleus. The Bohr model is a significant improvement over this as it quantifies the motion of electrons= Quantum Chemisty 1g circular orbits. The basic feature in this mod riscleiv atid electrons élnls'the centripetal for,’ ™ te fo around the nucleus by postulating CE needa coulombic attraction between the Keep the electrons in the circular orbit, that is, ir é Fie * erat a = m, x acceleration = m, x — Frcgrigat = ™, X 800% WAG 3 mx ekKS fs 7 nh re, the angular momentum (m, x v7) is quantised and equals > 2m Furthermot Combining the above, it follows that 2 eon, XE 4 “The Bohr model puts restrictions on the allowed orbits and for hydrogen, the radius of theo s ri stants, we obtain 7 is proportional to 7°. Substituting the fundamental con: (n?) x (52.9 x 10")m, where m is a positive integer. (Ly is 52.9 pm (or 0.529 A) and this value is known as ue is the unit of length in atomic units. In order to energies can be written as n= | refers to the first orbit whose radius the Bohr radius (designated as a,). This val obtain the energies, the sum of the kinetic and potential 1 ke? Ep =(5) a Since m,x— = kx r (1.2) (13)Bohr Model 3 Thus, the energy of an orbit arising from the Bohr model is given by Ey ~e (4) where R, = 13.6 eV = 2.18 = 10° J and is called the Rydberg constant. One electron volt represents the energy of an electron in an electric potential of one volt. Hence | electron volt = 1.60 = 10°" J. According to Eq. 1.4, there is a restriction regarding the values of n and hence the energy levels are quantised. However, circular orbits are the central postulate in the Bohr model which is untenable in modem quantum theories although the quantisation of electron energies is valid. Because the value of n is restricted to positive integers (n= 1, 2, 3...), not every value of n is allowed for the energy. In the modern quantum theory, the notion of electrons travelling in well-defined orbits around the nucleus is no longer acceptable. However, energy quantisation is still accepted. For hydrogen-like species, Eqs 1.1 and 1.4 are modified as (n')x (529 x10") Z | sod, =- 2x2 where Z denotes the number of electrons in the species. Problem 1.1 Show that the value of the Rydberg constant is 13.6 electron volts. The Rydberg constant can be written in terms of the permittivity of vacuum as = mass of electron = 9.109 x 10°! kg. x10%C as 13.6 electron volts. ising in atomic spectra. Further, this ple. An improvement of the Bohr4 Quantum Chemistry model was given by Sommerfeld, wherein the following improvisations were incorporated: Ea the ni (0) the allowed obits fr electrons can also be elliptical, was the ager 1922" (ii) another quantum number called the azimuthal Institute for Ady, the ‘number (J) was suggested to take into Btiidies in Cane ‘account, the geometry of the allowed orbits, and Denmark. Teese, (iii) for a given value of 7, several values of / were Constitutes an in T Mode permitted and these in turn lead to different shapes breakthrough in noe for the orbits. For n = 1, the orbit has a spherical development of atom, shape. When n = 2, the value of / can either be Structure. “a zero (spherical shape) or one (elliptical). Despite this improvement, the explanation of the hydrogen spectra using these two quantum numbers alone was not feasible. 1.21 ATOMIC SPECTRA Since discrete en spectroscopic data. with distinct spacing ‘at various regions of the el ergy levels are essential, it is imperative that their signatures be present j ‘The radiation emitted by hydrogen gas, for example, exhibits sh is tetween them. Such distinct lines have been experimentally ee lectromagnetic spectrum. These observations are of oe ignificance in the atomic structure and quantisation of energies. importance in view of their si lines was at variance with the concepts of classical physics. These lines The presence of these ‘are denoted by the numbers n and m, state) to m (final state) is given by 0" m", by ranges, the spectra can be clas: are caused due to transitions occurring between various energy states. If two energy levels the radiation emitted during the transition from n (initial sified asBlack Body Radiation 5 * Balmer series (Visible region, 350 nm to 750 nm): n= 2; m= 3,4, 5... The original Balmer spectra exhibited 4 lines at 410 nm, 434 nm, 486 nm and 656 nm. * Paschen series (near Infrared region, 1 mm to 700 nm): n= 3; m =4, 5, 6... * Brackett series (Infrared region, 2000 nm to 4000 nm): n = 4; m= 5, 6,7... * Phund series (far Infrared, 30 jum to 1000 um): n = 5; m= 6, 7, 8... 13 BLACK BODY RADIATION The concept of black body radiation plays a crucial role in demonstrating the inadequacy of classical mechanics with respect to the interaction of matter with radiation. If a material absorbs all the radiation incident upon it, it is considered an ideal black body. Consider a material possessing a hollow cavity such that when the radiation enters through the cavity, all of it gets absorbed. However, when the temperature of the material is increased, the radiation is emitted out of the cavity. Thus, the material now behaves as an emitter of radiation. The radiation arising out of the hollow cavity (black body) at high temperatures is known as black body radiation. The most noteworthy features of the black body radiation are as follows: * the energy density of the black body radiation is independent of the shape and nature of the cavity, * the temperature of the walls of the cavity dictates the energy density, and * there exists a maximum in the energy density which is influenced by the temperature. at different temperatures K