Rotational Structure in Molecular Infrared Spectra

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The relation between the rotational constants is given by. For other molecules, if the spectra can be resolved and individual transitions assigned both bond lengths and bond angles can be deduced. When this is not possible, as with most asymmetric tops, all that can be done is to fit the spectra to three moments of inertia calculated from an assumed molecular structure.

By varying the molecular structure the fit can be improved, giving a qualitative estimate of the structure. Isotopic substitution is invaluable when using this approach to the determination of molecular structure. The particular pattern of energy levels and, hence, of transitions in the rotational spectrum for a molecule is determined by its symmetry. A convenient way to look at the molecules is to divide them into four different classes, based on the symmetry of their structure.

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These are. Transitions between rotational states can be observed in molecules with a permanent electric dipole moment. Tetrahedral molecules such as CH 4 methane , which have both a zero dipole moment and isotropic polarizability, would not have a pure rotation spectrum but for the effect of centrifugal distortion; when the molecule rotates about a 3-fold symmetry axis a small dipole moment is created, allowing a weak rotation spectrum to be observed by microwave spectroscopy. Since these transitions are due to absorption or emission of a single photon with a spin of one, conservation of angular momentum implies that the molecular angular momentum can change by at most one unit.

For Raman spectra the molecules undergo transitions in which an incident photon is absorbed and another scattered photon is emitted. The general selection rule for such a transition to be allowed is that the molecular polarizability must be anisotropic , which means that it is not the same in all directions. The polarizability ellipsoid of spherical top molecules is in fact spherical so those molecules show no rotational Raman spectrum. For all other molecules both Stokes and anti-Stokes lines [notes 5] can be observed and they have similar intensities due to the fact that many rotational states are thermally populated.

The units used for rotational constants depend on the type of measurement. The relationship between these two units is derived from the expression. It follows that. The population of vibrationally excited states follows a Boltzmann distribution , so low-frequency vibrational states are appreciably populated even at room temperatures. As the moment of inertia is higher when a vibration is excited, the rotational constants B decrease.

Consequently, the rotation frequencies in each vibration state are different from each other. This can give rise to "satellite" lines in the rotational spectrum.

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Further, there is a fictitious force , Coriolis coupling , between the vibrational motion of the nuclei in the rotating non-inertial frame. However, as long as the vibrational quantum number does not change i. The Coriolis coupling is often negligible, too, if one is interested in low vibrational and rotational quantum numbers only.

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Historically, the theory of rotational energy levels was developed to account for observations of vibration-rotation spectra of gases in infrared spectroscopy , which was used before microwave spectroscopy had become practical. To a first approximation, the rotation and vibration can be treated as separable , so the energy of rotation is added to the energy of vibration. For example, the rotational energy levels for linear molecules in the rigid-rotor approximation are.

In reality, this expression has to be modified for the effects of anharmonicity of the vibrations, for centrifugal distortion and for Coriolis coupling. Because of the thermal population of the rotational states the P branch is slightly less intense than the R branch. Rotational constants obtained from infrared measurements are in good accord with those obtained by microwave spectroscopy, while the latter usually offers greater precision.

Spherical top molecules have no net dipole moment. 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.

Rotational–vibrational spectroscopy

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.

Rotational Structure In Molecular Infrared Spectra: By Carlo di Lauro | eBay

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. He is still working in the detailed interpretation of high resolution infrared spectra of ethane, and this activity has earned for him an international reputation in the community of planetary astronomers.

Beyond his scientific activity, Dr. Rotational Structure in Molecular Infrared Spectra. Carlo di Lauro.

IR Infrared Spectroscopy Review - 15 Practice Problems - Signal, Shape, Intensity, Functional Groups

Reviews basic theory and contemporary methods of vibration rotation absorption spectroscopy, including operational quantum mechanical methods, spherical tensor algebra, and group theoretical methods applied to molecular symmetry Covers sophisticated mathematical topics in simple, easy-to-read language Discusses methods and applications separately from basic theoretical arguments for quick reference.

Interaction of Matter and Light. Molecular Symmetry and Spectroscopy. Symmetry of Wavefunctions in VibrationRotation Spectroscopy.


Nuclear Spin Statistical Weights. Expansion and Transformations of the VibrationRotation Hamiltonian. Effects of Centrifugal Distortions. Since this is a pure rotation spectrum only the ground state value of B affects the spectrum. A slider to vary the centrifugal distortion constant is included with values in the range typical of these types of molecules, but the effect, which is just visible, only really shows up in quantitative calculations. Suggested "experiments" are i The B lower slider controls the value of B.

You will be able to observe that the spacing of the lines is approximately 4B. Note that, when one set of lines is completely missing slider moved to zero the pattern of line spacings is different from that when odd and even J are equally weighted. The first S line, S 0 , is present but the first O line, O 1 , is absent.

Here the additional possibility, that occurs in oxygen, of even J lines being missing is included right hand slider fully to the right. This happens because the oxygen nuclei are bosons but the ground state electronic wavefunction is antisymmetric.

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  • The interactive applet below calculates the infrared vibration rotation spectrum associated with a stretching vibration of a linear molecule. Click here for information concerning applets.

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    The calculation of the infrared spectrum is complete and includes the effects of centrifugal distortion, although these cannot be adjusted. If you download the programs the parameters of the control program can be changed to calculate any chosen spectrum for stretching of a linear molecule. Just set the parameter "control" to 1 and the remaining parameters are obvious. The following are suggested "experiments" for the infrared spectrum.

    Leaving the other sliders at their initial setting vary these two sliders. You should be able to observe that the spacing of the lines is approximately 2B and that a difference between the upper and lower state Bs leads to a convergence of the lines in one branch and a divergence in the other. The most common difference in the two B values leads to a the convergence being in the R branch. This gives a very useful means of estimating temperatures, especially in inaccessible situations such as in planetary atmospheres.

    Rotational Structure in Molecular Infrared Spectra Rotational Structure in Molecular Infrared Spectra
    Rotational Structure in Molecular Infrared Spectra Rotational Structure in Molecular Infrared Spectra
    Rotational Structure in Molecular Infrared Spectra Rotational Structure in Molecular Infrared Spectra
    Rotational Structure in Molecular Infrared Spectra Rotational Structure in Molecular Infrared Spectra
    Rotational Structure in Molecular Infrared Spectra Rotational Structure in Molecular Infrared Spectra

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