Physical Chemistry - Structure of Atom

SUMMARY

Atoms are the building blocks of elements. They are the smallest parts of an element that chemically react. The first atomic theory, proposed by John Dalton in 1808, regarded atom as the ultimate indivisible particle of matter. Towards the end of the nineteenth century, it was proved experimentally that atoms are divisible and consist of three fundamental particles: electrons, protons and neutrons. The discovery of sub-atomic particles led to the proposal of various atomic models to explain the structure of atom.

Thomson in 1898 proposed that an atom consists of uniform sphere of positive electricity with electrons embedded into it. This model in which mass of the atom is considered to be evenly spread over the atom was proved wrong by Rutherford’s famous alpha-particle scattering experiment in 1909. Rutherford concluded that atom is made of a tiny positively charged nucleus, at its centre with electrons revolving around it in circular orbits. Rutherford model, which resembles the solar system, was no doubt an improvement over Thomson model but it could not account for the stability of the atom i.e., why the electron does not fall into the nucleus. Further, it was also silent about the electronic structure of atoms i.e., about the distribution and relative energies of electrons around the nucleus. The difficulties of the Rutherford model were overcome by Niels Bohr in 1913 in his model of the hydrogen atom. Bohr postulated that electron moves around the nucleus in circular orbits. Only certain orbits can exist and each orbit corresponds to a specific energy. Bohr calculated the energy of electron in various orbits and for each orbit predicted the distance between the electron and nucleus. Bohr model, though offering a satisfactory model for explaining the spectra of the hydrogen atom, could not explain the spectra of multi-electron atoms. The reason for this was soon discovered. In Bohr model, an electron is regarded as a charged particle moving in a well defined circular orbit about the nucleus. The wave character of the electron is ignored in Bohr’s theory. An orbit is a clearly defined path and this path can completely be defined only if both the exact position and the exact velocity of the electron at the same time are known. This is not possible according to the Heisenberg uncertainty principle. Bohr model of the hydrogen atom, therefore, not only ignores the dual behaviour of electron but also contradicts Heisenberg uncertainty principle.

Erwin Schrödinger, in 1926, proposed an equation called Schrödinger equation to describe the electron distributions in space and the allowed energy levels in atoms. This equation incorporates de Broglie’s concept of wave-particle duality and is consistent with Heisenberg uncertainty principle. When Schrödinger equation is solved for the electron in a hydrogen atom, the solution gives the possible energy states the electron can occupy [and the corresponding wave function(s) (ψ) (which in fact are the mathematical functions) of the electron associated with each energy state]. These quantized energy states and corresponding wave functions which are characterized by a set of three quantum numbers (principal quantum number n, azimuthal quantum number l and magnetic quantum number ml ) arise as a natural consequence in the solution of the Schrödinger equation. The restrictions on the values of these three quantum numbers also come naturally from this solution. The quantum mechanical model of the hydrogen atom successfully predicts all aspects of the hydrogen atom spectrum including some phenomena that could not be explained by the Bohr model.

According to the quantum mechanical model of the atom, the electron distribution of an atom containing a number of electrons is divided into shells. The shells, in turn, are thought to consist of one or more subshells and subshells are assumed to be composed of one or more orbitals, which the electrons occupy. While for hydrogen and hydrogen like systems (such as He+ , Li2+ etc.) all the orbitals within a given shell have same energy, the energy of the orbitals in a multi-electron atom depends upon the values of n and l: The lower the value of (n + l ) for an orbital, the lower is its energy. If two orbitals have the same (n + l ) value, the orbital with lower value of n has the lower energy. In an atom many such orbitals are possible and electrons are filled in those orbitals in order of increasing energy in accordance with Pauli exclusion principle (no two electrons in an atom can have the same set of four quantum numbers) and Hund’s rule of maximum multiplicity (pairing of electrons in the orbitals belonging to the same subshell does not take place until each orbital belonging to that subshell has got one electron each, i.e., is singly occupied). This forms the basis of the electronic structure of atoms.