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A pure rotational spectrum cannot be observed by absorption or emission spectroscopy because there is no permanent dipole moment whose rotation can be accelerated by the electric field of an incident photon. Also the polarizability is isotropic, so that pure rotational transitions cannot be observed by Raman spectroscopy either. Nevertheless, rotational constants can be obtained by ro-vibrational spectroscopy. This occurs when a molecule is polar in the vibrationally excited state. For example, the molecule methane is a spherical top but the asymmetric C-H stretching band shows rotational fine structure in the infrared spectrum, illustrated in rovibrational coupling.

This spectrum is also interesting because it shows clear evidence of Coriolis coupling in the asymmetric structure of the band. The rigid rotor is a good starting point from which to construct a model of a rotating molecule. It is assumed that component atoms are point masses connected by rigid bonds.

A linear molecule lies on a single axis and each atom moves on the surface of a sphere around the centre of mass. J defines the magnitude of the rotational angular momentum, and M its component about an axis fixed in space, such as an external electric or magnetic field. In the absence of external fields, the energy depends only on J. Under the rigid rotor model, the rotational energy levels, F J , of the molecule can be expressed as,.

Selection rules dictate that during emission or absorption the rotational quantum number has to change by unity; i. Thus, the locations of the lines in a rotational spectrum will be given by. The dashed lines show how these transitions map onto features that can be observed experimentally. Frequency or wavenumber units can also be used for the x axis of this plot. The probability of a transition taking place is the most important factor influencing the intensity of an observed rotational line.

This probability is proportional to the population of the initial state involved in the transition. The population of a rotational state depends on two factors. This factor decreases as J increases. This factor increases as J increases. Combining the two factors [18]. The maximum relative intensity occurs at [19] [notes 6].

The diagram at the right shows an intensity pattern roughly corresponding to the spectrum above it. When a molecule rotates, the centrifugal force pulls the atoms apart. To account for this a centrifugal distortion correction term is added to the rotational energy levels of the diatomic molecule. In consequence, the spacing between lines is not constant, as in the rigid rotor approximation, but decreases with increasing rotational quantum number. An assumption underlying these expressions is that the molecular vibration follows simple harmonic motion.

If anharmonicity is to be taken into account, terms in higher powers of J should be added to the expressions for the energy levels and line positions. The electric dipole moment of the dioxygen molecule, O 2 is zero, but the molecule is paramagnetic with two unpaired electrons so that there are magnetic-dipole allowed transitions which can be observed by microwave spectroscopy. The 16 O nucleus has zero nuclear spin angular momentum, so that symmetry considerations demand that K have only odd values.

For symmetric rotors a quantum number J is associated with the total angular momentum of the molecule. The third quantum number, K is associated with rotation about the principal rotation axis of the molecule. In the absence of an external electrical field, the rotational energy of a symmetric top is a function of only J and K and, in the rigid rotor approximation, the energy of each rotational state is given by. The term in D JK has the effect of removing degeneracy present in the rigid rotor approximation, with different K values.

The quantum number J refers to the total angular momentum, as before. Since there are three independent moments of inertia, there are two other independent quantum numbers to consider, but the term values for an asymmetric rotor cannot be derived in closed form. They are obtained by individual matrix diagonalization for each J value. Formulae are available for molecules whose shape approximates to that of a symmetric top. The water molecule is an important example of an asymmetric top.

For this reason far infrared spectrometers have to be freed of atmospheric water vapour either by purging with a dry gas or by evacuation. The spectrum has been analyzed in detail. In that case, coupling of nuclear spin angular momentum with rotational angular momentum causes splitting of the rotational energy levels. The effect is one type of hyperfine splitting. The energies of the sub-levels are proportional to the nuclear quadrupole moment and a function of F and J. Thus, observation of nuclear quadrupole splitting permits the magnitude of the nuclear quadrupole moment to be determined.

The selection rule for rotational transitions becomes [29]. The extent of splitting depends on the square of the electric field strength and the square of the dipole moment of the molecule. A similar removal of degeneracy will occur when a paramagnetic molecule is placed in a magnetic field, an instance of the Zeeman effect. Most species which can be observed in the gaseous state are diamagnetic. Exceptions are odd-electron molecules such as nitric oxide , NO, nitrogen dioxide , NO 2 , some chlorine oxides and the hydroxyl radical.

The Zeeman effect has been observed with dioxygen , O 2 [32]. Molecular rotational transitions can also be observed by Raman spectroscopy. Rotational transitions are Raman-allowed for any molecule with an anisotropic polarizability which includes all molecules except for spherical tops. This means that rotational transitions of molecules with no permanent dipole moment, which cannot be observed in absorption or emission, can be observed, by scattering, in Raman spectroscopy.


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Very high resolution Raman spectra can be obtained by adapting a Fourier Transform Infrared Spectrometer. An example is the spectrum of 15 N 2. It shows the effect of nuclear spin, resulting in intensities variation of in adjacent lines. A bond length of The great majority of contemporary spectrometers use a mixture of commercially available and bespoke components which users integrate according to their particular needs.

Instruments can be broadly categorised according to their general operating principles. Although rotational transitions can be found across a very broad region of the electromagnetic spectrum , fundamental physical constraints exist on the operational bandwidth of instrument components. It is often impractical and costly to switch to measurements within an entirely different frequency region. A microwave spectrometer can be most simply constructed using a source of microwave radiation, an absorption cell into which sample gas can be introduced and a detector such as a superheterodyne receiver.

A spectrum can be obtained by sweeping the frequency of the source while detecting the intensity of transmitted radiation. A simple section of waveguide can serve as an absorption cell. An important variation of the technique in which an alternating current is applied across electrodes within the absorption cell results in a modulation of the frequencies of rotational transitions. Property law. Conveyancing law. Housing law. Personal property law. Social law. Charity law. Consumer protection law. Mental health law. Social insurance law. Corporate tax. Personal tax. Personal injury.

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