Selection rule in the context of Zeeman effect

In vibrational spectroscopy, an overtone band is the spectral band that occurs in a vibrational spectrum of a molecule when the molecule makes a transition from the ground state (v=0) to the second excited state (v=2), where v is the vibrational quantum number (a non-negative integer) obtained from solving the Schrödinger equation for the molecule.

Generally, in order to study the vibrational spectra of molecules, chemical bond vibrations are assumed to be approximable as simple harmonic oscillators. Thus a quadratic potential is used in the Schrödinger equation to solve for the vibrational energy eigenstates and their eigenvalues.These energy states are quantized, meaning they can assume only some "discrete" values of energy. When electromagnetic radiation is shined on a sample, the molecules can absorb energy from the radiation and change their vibrational energy state. However, the molecules can absorb energy from radiation only under certain condition, namely- there should be a change in the electric dipole moment of the molecule when it is vibrating. This change in the electric dipole moment of the molecule leads to the transition dipole moment of the molecule, for transition from the lower to higher energy state, being non-zero which is an essential condition for any transition to take place in the vibrational state of the molecule (due to selection rules).

In mathematics and geometry, a discrete symmetry is a symmetry that describes non-continuous changes in a system. For example, a square possesses discrete rotational symmetry, as only rotations by multiples of right angles will preserve the square's original appearance. Discrete symmetries sometimes involve some type of 'swapping', these swaps usually being called reflections or interchanges. In mathematics and theoretical physics, a discrete symmetry is a symmetry under the transformations of a discrete group—e.g. a topological group with a discrete topology whose elements form a finite or a countable set.

One of the most prominent discrete symmetries in physics is parity symmetry. It manifests itself in various elementary physical quantum systems, such as quantum harmonic oscillator, electron orbitals of Hydrogen-like atoms by forcing wavefunctions to be even or odd. This in turn gives rise to selection rules that determine which transition lines are visible in atomic absorption spectra.

Rotational–vibrational spectroscopy is a branch of molecular spectroscopy that is concerned with infrared and Raman spectra of molecules in the gas phase. Transitions involving changes in both vibrational and rotational states can be abbreviated as rovibrational (or ro-vibrational) transitions. When such transitions emit or absorb photons (electromagnetic radiation), the frequency is proportional to the difference in energy levels and can be detected by certain kinds of spectroscopy. Since changes in rotational energy levels are typically much smaller than changes in vibrational energy levels, changes in rotational state are said to give fine structure to the vibrational spectrum. For a given vibrational transition, the same theoretical treatment as for pure rotational spectroscopy gives the rotational quantum numbers, energy levels, and selection rules. In linear and spherical top molecules, rotational lines are found as simple progressions at both higher and lower frequencies relative to the pure vibration frequency. In symmetric top molecules the transitions are classified as parallel when the dipole moment change is parallel to the principal axis of rotation, and perpendicular when the change is perpendicular to that axis. The ro-vibrational spectrum of the asymmetric rotor water is important because of the presence of water vapor in the atmosphere.