vibrational spectroscopy Infrared spectroscopy (IR spectroscopy or vibrational spectroscopy) is the measurement of the interaction of infrared radiation with matter by absorption, emission, or reflection. It is used to study and identify chemical substances or functi ...

, 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 In quantum mechanics, an excited state of a system (such as an atom, molecule or nucleus) is any quantum state of the system that has a higher energy than the ground state (that is, more energy than the absolute minimum). Excitation refers t ...

(v=2), where v is the

vibrational quantum number A molecular vibration is a periodic motion of the atoms of a molecule relative to each other, such that the center of mass of the molecule remains unchanged. The typical vibrational frequencies range from less than 1013 Hz to approximately 1014 Hz ...

(a non-negative integer) obtained from solving the

Schrödinger equation The Schrödinger equation is a linear partial differential equation that governs the wave function of a quantum-mechanical system. It is a key result in quantum mechanics, and its discovery was a significant landmark in the development of th ...

for the molecule. Generally, in order to study the vibrational spectra of molecules,

chemical bond A chemical bond is a lasting attraction between atoms or ions that enables the formation of molecules and crystals. The bond may result from the electrostatic force between oppositely charged ions as in ionic bonds, or through the sharing o ...

vibrations are assumed to be approximable as simple

harmonic oscillator In classical mechanics, a harmonic oscillator is a system that, when displaced from its Mechanical equilibrium, equilibrium position, experiences a restoring force ''F'' Proportionality (mathematics), proportional to the displacement ''x'': \v ...

s. 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 Discrete may refer to: *Discrete particle or quantum in physics, for example in quantum theory *Discrete device, an electronic component with just one circuit element, either passive or active, other than an integrated circuit *Discrete group, a ...

" 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 The electric dipole moment is a measure of the separation of positive and negative electrical charges within a system, that is, a measure of the system's overall polarity. The SI unit for electric dipole moment is the coulomb-meter (C⋅m). The ...

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). Importantly, under the simple harmonic approximation, it can be shown that the transition dipole moment is non-zero only for transitions where ∆v=±1. Hence for an ideal, simple-harmonically vibrating bond, the vibrational spectrum contains no overtones. Of course, real molecules do not vibrate perfectly harmonically, because a bond's potential is not precisely quadratic but better approximated as a

Morse potential The Morse potential, named after physicist Philip M. Morse, is a convenient interatomic interaction model for the potential energy of a diatomic molecule. It is a better approximation for the vibrational structure of the molecule than the qua ...

. Solving the Schrödinger equation with the Morse potential for the molecule under consideration yields vibrational energy eigenstates with the interesting property that when one calculates transition dipole moments for various vibrational energy level transitions, the transition dipole moment is not zero for the transitions where ∆v=±2,±3,±4, etc. Thus, for real molecules, the allowed transitions are those for which ∆v=±1,±2,±3,±4, etc. The overtone band observed in the

IR spectrum Infrared spectroscopy (IR spectroscopy or vibrational spectroscopy) is the measurement of the interaction of infrared radiation with matter by absorption, emission, or reflection. It is used to study and identify chemical substances or function ...

is one such transition with ∆v=2, from v=0 to v=2 energy state. It has been experimentally found that the intensity of the overtone band is very low compared to the fundamental band, validating the harmonic approximation.

References

*C.N.Banwell and E.M.McCash:Fundamentals of Molecular Spectroscopy, Tata McGraw-Hill Fourth Edition Raman spectroscopy Infrared spectroscopy {{spectroscopy-stub Book name Y. R. Sharma

See also

References