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OverviewRo-vibrational spectroscopy concerns molecules in the gas phase. There are sequences of quantized rotational levels associated with both the ground and excited vibrational states. The spectra are often resolved into lines due to transitions from one rotational level in the ground vibrational state to one rotational level in the vibrationally excited state. The lines corresponding to a given vibrational transition form a band.
In the simplest cases the part of the infrared spectrum involving vibrational transitions with the same rotational quantum number (ΔJ = 0) in ground and excited states is called the Q-branch. On the high frequency side of the Q-branch the energy of rotational transitions is added to the energy of the vibrational transition. This is known as the R-branch of the spectrum for ΔJ = +1. The P-branch for ΔJ = −1 lies on the low wavenumber side of the Q branch. The appearance of the R-branch is very similar to the appearance of the pure rotation spectrum, and the P-branch appears as a nearly mirror image of the R-branch.[note 1]
The appearance of rotational fine structure is determined by the symmetry of the molecular rotors which are classified, in the same way as for pure rotational spectroscopy, into linear molecules, spherical-, symmetric- and asymmetric- rotor classes. The quantum mechanical treatment of rotational fine structure is the same as for pure rotation.
A general convention is to label quantities that refer to the vibrational ground and excited states of a transition with double prime and single prime, respectively. For example, the rotational constant for the ground state is written as and that of the excited state as Also, these constants are expressed in the molecular spectroscopist's units of cm−1. so that in this article corresponds to in the definition of rotational constant at Rigid rotor.
Method of combination differencesNumerical analysis of ro-vibrational spectral data would appear to be complicated by the fact that the wavenumber for each transition depends on two rotational constants, and . However combinations which depend on only one rotational constant are found by subtracting wavenumbers of pairs of lines (one in the P-branch and one in the R-branch) which have either the same lower level or the same upper level. For example, in a diatomic molecule the line denoted P(J + 1) is due to the transition (v = 0, J + 1) → (v = 1, J), and the line R(J − 1) is due to the transition (v = 0, J − 1) → (v = 1, J). The difference between the two wavenumbers corresponds to the energy difference between the (J + 1) and (J − 1) levels of the lower vibrational state and denoted by since it is the difference between levels differing by two units of J. If centrifugal distortion is included, it is given by
Similarly the difference R(J) − P(J) depends only on the constants B′ and D′ for the excited vibrational state (v = 1), and B′ can be used to determine the internuclear distance in that state (which is inaccessible to pure rotational spectroscopy).
Heteronuclear diatomic molecules
Diatomic molecules with the general formula AB have one normal mode of vibration involving stretching of the A-B bond. The vibrational term values ,[note 3] for an anharmonic oscillator are given, to a first approximation, by
When the molecule is in the gas phase, it can rotate about an axis, perpendicular to the molecular axis, passing through the centre of mass of the molecule. The rotational energy is also quantized, with term values to a first approximation given by
The selection rule for electric dipole allowed ro-vibrational transitions, in the case of a diamagnetic diatomic molecule is
- Both the vibrational and rotational quantum numbers must change. The transition : (Q-branch) is forbidden
- The energy change of rotation can be either subtracted from or added to the energy change of vibration, giving the P- and R- branches of the spectrum, respectively.
where positive m values refer to the R-branch and negative values refer to the P-branch. The term ω0 gives the position of the (missing) Q-branch, the term implies an progression of equally spaced lines in the P- and R- branches, but the third term, shows that the separation between adjacent lines changes with changing rotational quantum number. When is greater than , as is usually the case, as J increases the separation between lines decreases in the R-branch and increases in the P-branch. Analysis of data from the infrared spectrum of carbon monoxide, gives value of of 1.915 cm−1 and of 1.898 cm−1. The bond lengths are easily obtained from these constants as r0 = 113.3 pm, r1 = 113.6 pm. These bond lengths are slightly different from the equilibrium bond length. This is because there is zero-point energy in the vibrational ground state, whereas the equilibrium bond length is at the minimum in the potential energy curve. The relation between the rotational constants is given by
Nitric oxide, NO, is a special case as the molecule is paramagnetic, with one unpaired electron. Coupling of the electron spin angular momentum with the molecular vibration causes lambda-doubling[note 5] with calculated harmonic frequencies of 1904.03 and 1903.68 cm−1. Rotational levels are also split.
Homonuclear diatomic moleculesThe quantum mechanics for diatomic molecules such as dinitrogen, N2, and fluorine, F2, is qualitatively the same as for heteronuclear diatomic molecules, but the selection rules governing transitions are different. Since the electric dipole moment of these molecules is zero, the fundamental vibrational transition is electric-dipole-forbidden. However, a weak quadrupole-allowed spectrum of N2 can be observed when using long path-lengths both in the laboratory and in the atmosphere. The spectra of these molecules can be observed by Raman spectroscopy because the molecular vibration is Raman-allowed.
Dioxygen is a special case as the molecule is paramagnetic so magnetic-dipole-allowed transitions can be observed in the infrared. The unit electron spin has three spatial orientations with respect to the molecular rotational angular momentum vector, N,[note 6] so that each rotational level is split into three states with total angular momentum (molecular rotation plus electron spin) , J = N + 1, N, and N - 1, each J state of this so-called p-type triplet arising from a different orientation of the spin with respect to the rotational motion of the molecule. Selection rules for magnetic dipole transitions allow transitions between successive members of the triplet (ΔJ = ±1) so that for each value of the rotational angular momentum quantum number N there are two allowed transitions. The 16O nucleus has zero nuclear spin angular momentum, so that symmetry considerations demand that N may only have odd values.
Raman spectra of diatomic moleculesThe selection rule is
For homonuclear diatomics, nuclear spin statistical weights lead to alternating line intensities between even- and odd- levels. For nuclear spin I = 1/2 as in 1H2 and 19F2 the intensity alternation is 1:3. For 2H2 and 14N2, I=1 and the statistical weights are 6 and 3 so that the even- levels are twice as intense. For 16O2 (I=0) all transitions with even values of are forbidden.
Polyatomic linear molecules
These molecules fall into two classes, according to symmetry: centrosymmetric molecules with point group D∞h, such as carbon dioxide, CO2, and ethyne or acetylene, HCCH; and non-centrosymmetric molecules with point group C∞v such as hydrogen cyanide, HCN, and nitrous oxide, NNO. Centrosymmetric linear molecules have a dipole moment of zero, so do not show a pure rotation spectrum in the infrared or microwave regions. On the other hand, in certain vibrational excited states the molecules do have a dipole moment so that a ro-vibrational spectrum can be observed in the infrared.
The spectra of these molecules are classified according to the direction of the dipole moment change vector. When the vibration induces a dipole moment change pointing along the molecular axis the term parallel is applied, with the symbol . When the vibration induces a dipole moment pointing perpendicular to the molecular axis the term perpendicular is applied, with the symbol . In both cases the P- and R- branch wavenumbers follow the same trend as in diatomic molecules. The two classes differ in the selection rules that apply to ro-vibrational transitions. For parallel transitions the selection rule is the same as for diatomic molecules, namely, the transition corresponding to the Q-branch is forbidden. An example is the C-H stretching mode of hydrogen cyanide.
For a perpendicular vibration the transition ΔJ=0 is allowed. This means that the transition is allowed for the molecule with the same rotational quantum number in the ground and excited vibrational state, for all the populated rotational states. This makes for an intense, relatively broad, Q-branch consisting of overlapping lines due to each rotational state. The N-N-O bending mode of nitrous oxide, at ca. 590 cm−1 is an example.
The spectra of centrosymmetric molecules exhibit alternating line intensities due to quantum state symmetry effects, since rotation of the molecule by 180° about a 2-fold rotation axis is equivalent to exchanging identical nuclei. In carbon dioxide, the oxygen atoms of the predominant isotopic species 12C16O2 have spin zero and are bosons, so that the total wavefunction must be symmetric when the two 16O nuclei are exchanged. The nuclear spin factor is always symmetric for two spin-zero nuclei, so that the rotational factor must also be symmetric which is true only for even-J levels. The odd-J rotational levels cannot exist and the allowed vibrational bands consist of only absorption lines from even-J initial levels. The separation between adjacent lines in the P- and R- branches is close to 4B rather than 2B as alternate lines are missing. For acetylene the hydrogens of 1H12C12C1H have spin ½ and are fermions, so the total wavefunction is antisymmetric when two 1H nuclei are exchanged. As is true for ortho and para hydrogen the nuclear spin function of the two hydrogens has three symmetric ortho states and one antisymmetric para states. For the three ortho states, the rotational wave function must be antisymmetric corresponding to odd J, and for the one para state it is symmetric corresponding to even J. The population of the odd J levels are therefore three times higher than the even J levels, and alternate line intensities are in the ratio 3:1.
Spherical top molecules
These molecules have equal moments of inertia about any axis, and belong to the point groups Td (tetrahedral AX4) and Oh (octahedral AX6). Molecules with these symmetries have a dipole moment of zero, so do not have a pure rotation spectrum in the infrared or microwave regions.
Tetrahedral molecules such as methane, CH4, have infrared-active stretching and bending vibrations, belonging to the T2 (sometimes written as F2) representation.[note 7] These vibrations are triply degenerate and the rotational energy levels have three components separated by the Coriolis interaction. The rotational term values are given, to a first order approximation, by
Symmetric top moleculesThese molecules have a unique principal rotation axis of order 3 or higher. There are two distinct moments of inertia and therefore two rotational constants. For rotation about any axis perpendicular to the unique axis, the moment of inertia is and the rotational constant is , as for linear molecules. For rotation about the unique axis, however, the moment of inertia is and the rotational constant is . Examples include ammonia, NH3 and methyl chloride, CH3Cl (both of molecular symmetry described by point group C3v), boron trifluoride, BF3 and phosphorus pentachloride, PCl5 (both of point group D3h), and benzene, C6H6 (point group D6h).
For symmetric rotors a quantum number J is associated with the total angular momentum of the molecule. For a given value of J, there is a 2J+1- fold degeneracy with the quantum number, M taking the values +J ...0 ... -J. The third quantum number, K is associated with rotation about the principal rotation axis of the molecule. As with linear molecules, transitions are classified as parallel, or perpendicular,, in this case according to the direction of the dipole moment change with respect to the principal rotation axis. A third category involves certain overtones and combination bands which share the properties of both parallel and perpendicular transitions. The selection rules are
- If K ≠ 0, then ΔJ = 0, ±1 and ΔK = 0
- If K = 0, then ΔJ = ±1 and ΔK = 0
- ΔJ = 0, ±1 and ΔK = ±1
Parallel bandsThe C-Cl stretching vibration of methyl chloride, CH3Cl, gives a parallel band since the dipole moment change is aligned with the 3-fold rotation axis. The line spectrum shows the sub-structure of this band rather clearly; in reality, very high resolution spectroscopy would be needed to resolve the fine structure fully. Allen and Cross show parts of the spectrum of CH3D and give a detailed description of the numerical analysis of the experimental data.
Perpendicular bandsThe selection rule for perpendicular bands give rise to more transitions than with parallel bands. A band can be viewed as a series of sub-structures, each with P, Q and R branches. The Q-branches are separated by approximately 2(A′-B′). The asymmetric HCH bending vibration of methyl chloride is typical. It shows a series of intense Q-branches with weak rotational fine structure. Analysis of the spectra is made more complicated by the fact that the ground-state vibration is bound, by symmetry, to be a degenerate vibration, which means that Coriolis coupling also affects the spectrum.
Hybrid bandsOvertones of a degenerate fundamental vibration have components of more than one symmetry type. For example, the first overtone of a vibration belonging to the E representation in a molecule like ammonia, NH3, will have components belonging to A1 and E representations. A transition to the A1 component will give a parallel band and a transition to the E component will give perpendicular bands; the result is a hybrid band.
Inversion in ammonia
The vibrational ground state (v = 0) is also doubled although the energy difference is much smaller, and the transition between the two levels can be measured directly in the microwave region, at ca. 24 Ghz (0.8 cm−1). This transition is historically significant and was used in the ammonia MASER, the fore-runner of the LASER.
Asymmetric top molecules
Asymmetric top molecules have at most one or more 2-fold rotation axes. There are three unequal moments of inertia about three mutually perpendicular principal axes. The spectra are very complex. The transition wavenumbers cannot be expressed in terms of an analytical formula but can be calculated using numerical methods.
The water molecule is an important example of this class of molecule, particularly because of the presence of water vapor in the atmosphere. The low-resolution spectrum shown in green illustrates the complexity of the spectrum. At wavelengths greater than 10 μm (or wavenumbers less than 1000 cm−1) the absorption is due to pure rotation. The band around 6.3 μm (1590 cm−1) is due to the HOH bending vibration; the considerable breadth of this band is due to the presence of extensive rotational fine structure. High-resolution spectra of this band are shown in Allen and Cross, p 221. The symmetric and asymmetric stretching vibrations are close to each other, so the rotational fine structures of these bands overlap. The bands at shorter wavelength are overtones and combination bands, all of which show rotational fine structure. Medium resolution spectra of the bands around 1600 cm−1 and 3700 cm−1 are shown in Banwell and McCash, p91.
Ro-vibrational bands of asymmetric top molecules are classed as A-, B- or C- type for transitions in which the dipole moment change is along the axis of smallest moment of inertia to the highest.
Experimental methodsRo-vibrational spectra are usually measured at high spectral resolution. In the past, this was achieved by using an echelle grating as the spectral dispersion element in a grating spectrometer. This is a type of diffraction grating optimized to use higher diffraction orders. The resolving power of an FTIR spectrometer depends on the maximum retardation of the moving mirror. For example, to achieve a resolution of 0.1 cm−1, the moving mirror must have a maximum displacement of 10 cm from its position at zero path difference. Connes measured the vibration-rotation spectrum of Venusian CO2 at this resolution. A spectrometer with 0.001 cm−1 resolution is now available commercially. The throughput advantage of FTIR is important for high-resolution spectroscopy as the monochromator in a dispersive instrument with the same resolution would have very narrow entrance and exit slits.
When measuring the spectra of gases it is relatively easy to obtain very long path-lengths by using a multiple reflection cell. This is important because it allows the pressure to be reduced so as to minimize pressure broadening of the spectral lines, which may degrade resolution. Path lengths up to 20m are commercially available.