Rotational transitions spectroscopy

Every electronic transition in a molecule is accompanied by changes in vibrational and rotational states. Generally, in the liquid state, individual rotational transitions are not resolved, so that electronic spectra consist of broad bands from overlapping rotational transitions. Spectroscopy on the gas phase can often resolve individual rotational as well as vibrational transitions. 

Electron-impact energy-loss spectroscopy (EELS) differs from other electron spectroscopies in that it is possible to observe transitions to states below the first ionization edge electronic transitions to excited states of the neutral, vibrational and even rotational transitions can be observed. This is a consequence of the detected electrons not originating in the sample. Conversely, there is a problem when electron impact induces an ionizing transition. For each such event there are two outgoing electrons. To precisely account for the energy deposited in the target, the two electrons must be measured in coincidence. 

We have seen in Section 5.2.1.4 that there is a stack of rotational energy levels associated with all vibrational levels. In rotational spectroscopy we observe transitions between rotational energy levels associated with the same vibrational level (usually v = 0). In vibration-rotation spectroscopy we observe transitions between stacks of rotational energy levels associated with two different vibrational levels. These transitions accompany all vibrational transitions but, whereas vibrational transitions may be observed even when the sample is in the liquid or solid phase, the rotational transitions may be observed only in the gas phase at low pressure and usually in an absorption process. 

Raman scattering is normally of such very low intensity that gas phase Raman spectroscopy is one of the more difficult techniques. This is particularly the case for vibration-rotation Raman spectroscopy since scattering involving vibrational transitions is much weaker than that involving rotational transitions, which were described in Sections 5.3.3 and 5.3.5. For this reason we shall consider here only the more easily studied infrared vibration-rotation spectroscopy which must also be investigated in the gas phase (or in a supersonic jet, see Section 9.3.8). 

Table 10.4 lists the rate parameters for the elementary steps of the CO + NO reaction in the limit of zero coverage. Parameters such as those listed in Tab. 10.4 form the highly desirable input for modeling overall reaction mechanisms. In addition, elementary rate parameters can be compared to calculations on the basis of the theories outlined in Chapters 3 and 6. In this way the kinetic parameters of elementary reaction steps provide, through spectroscopy and computational chemistry, a link between the intramolecular properties of adsorbed reactants and their reactivity Statistical thermodynamics furnishes the theoretical framework to describe how equilibrium constants and reaction rate constants depend on the partition functions of vibration and rotation. Thus, spectroscopy studies of adsorbed reactants and intermediates provide the input for computing equilibrium constants, while calculations on the transition states of reaction pathways, starting from structurally, electronically and vibrationally well-characterized ground states, enable the prediction of kinetic parameters. 

Microwave spectroscopy is generally defined as the high-resolution absorption spectroscopy of molecular rotational transitions in the gas phase. Microwave spectroscopy observes the transitions between the quantised rotational sublevels of a given vibrational state in the electronic ground state of free molecules. Molecular... 

For liquids, the collision rate is close to 1030 collisions s 1. Microwave spectroscopy, which studies molecular rotation, only uses dilute gases to obtain pure rotational states of sufficient lifetime. Rotational transitions are broadened by molecular collisions, because the pressure is close to a few tenths of a bar, as shown in Fig. 1.6. 

Figure 0.2 Direct overtone spectroscopy of C2H2 using Fourier transform spectroscopy. Here, at high resolution, the entire band of rotational transitions, which accompany a given vibrational transition, can be resolved. Here the band, in the visible range, corresponding to the direct excitation of v = 5 of the v3 stretch mode is shown. (Adapted from Herman et al., 1991. See also Scherer, Lehmann, and Klemperer, 1983, and Figure 8.4.)...

Photoelectron spectroscopy (PES, a non-mass spectral technique) [87] has proven to be very useful in providing information not only about ionization potentials, but also about the electronic and vibrational structure of atoms and molecules. Energy resolutions reported from PES are in the order of 10-15 meV. The resolution of PES still prevents the observation of rotational transitions, [79] and to overcome these limitations, PES has been further improved. In brief, the principle of zero kinetic energy photoelectron spectroscopy (ZEKE-PES or just ZEKE, also a nonmass spectral technique) [89-91] is based on distinguishing excited ions from ground state ions. 

The earliest experiments with lasers in absorption spectroscopy were performed with the high-gain infrared line X = 3.39p of the He-Ne laser the first gas laser Several authors Miscovered that this laser line is absorbed by many hydrocarbon molecules, causing a vibrational-rotational transition in a band which belongs to the excitation of a C-H stretching vibration . ... 

In microwave spectroscopy, the energy of the radiation lies in the range of fractions of a cm-1 through several cm 1 such energies are adequate to excite rotational motions of molecules but are not high enough to excite any but the weakest vibrations (e.g., those of weakly bound Van der Waals complexes). In rotational transitions, the electronic and vibrational states are thus left unchanged by the excitation process hence /ej = /ef and %Yl... 

Absorption spectroscopy. OH undergoes an allowed transition between its X2n ground state and the first electronically excited A2 5. state. Because it is a small species, absorption lines due to the individual vibrational and rotational transitions can be resolved experimentally. As a result, it has a very characteristic banded absorption structure around 308 nm whose features make it an ideal candidate for DOAS measurements. 

Microwave (rotational) spectra are very complex, even for diatomic molecules, and give little useful information on organic molecules, which are relatively large. Rotational transitions are often responsible for the broadness of infrared (IR) bands, since each vibrational transition has a number of rotational transitions associated with it. The use of microwave spectroscopy is extremely rare in organic chemistry, and it too will be discussed no further here. 

Over the last years we have explored several advanced techniques for high-resolution rotational coherence spectroscopy (RCS [1]) in order to study the structures of molecules and clusters in the gas phase [2]. We have provided spectroscopic examples demonstrating (i) mass-selectivity (Fig. 1, [3]), (ii) that the rotational constants of the ground and electronic excited states can be obtained independently with high precision (lO MO"5, [4]), (iii) that the transition dipole moment alignment, (iv) centrifugal distortion constants, and (v) information on the polarizability tensor can be obtained (Fig.l, [5]). Here we review results pertaining to points (i), (ii), (iv) and (v) [2,3,5],... 

Rotational Raman spectroscopy is a powerful tool to determine the structures of molecules. In particular, besides electron diffraction, it is the only method that can probe molecules that exhibit no electric dipole moment for which microwave or infrared data do not exist. Although rotational constants can be extracted from vibrational spectra via combination differences or by known correction factors of deuterated species the method is the only one that yields directly the rotational constant B0. However for cyclopropane, the rotational microwave spectrum, recording the weak AK=3 transitions could be measured by Brupacher [20],... 

Figure 18-19 Laser spectroscopy of water vapor showing individual rotational transitions of H2I60, H2170, and H2,8O.The upper trace is from a standard water sample and the lower trace is from an unknown. Relative peak areas In the two spectra provide isotope ratios to an accuracy of 0.1 %. [E. R. Th. Kerstel, R. van Trlgt,...

High speed emission spectroscopy has been used to study free radicals and positive, negative, and multiple ions produced in explosions and flames. Many excited states would exist for many different species from coal subjected to high energy. Complex spectra would result. The combination of electronic-vibration-rotation transitions observable in emission spectroscopy... 

The detection and identification of molecules in interstellar space is possible by millimeter wave spectroscopy. The independent synthesis and detection of such reactive species, e.g. by flash vaccuum thermolysis and mm wave spectroscopy, provides proof for their cosmochemical existence. The detection of the J 6 —> 7 rotational transition in the decomposition products of t-Bu2HSi—NH(CH2— C=CH) indicated the formation of HNSi (Table 20)333. 

For any vibrational mode, the relative intensities of Stokes and anti-Stokes scattering depend only on the temperature. Measurement of this ratio can be used for temperature measurement, although this application is not commonly encountered in pharmaceutical or biomedical applications. Raman scattering based on rotational transitions in the gas phase and low energy (near-infrared) electronic transitions in condensed phases can also be observed. These forms of Raman scattering are sometimes used by physical chemists. However, as a practical matter, to most scientists, Raman spectroscopy means and will continue to mean vibrational Raman spectroscopy. 

The principal reaction discussed above forms oxygen molecules in high vibrational levels of the ground state. This is chemi-excitation but is not chemiluminescence vibration-rotation transitions of homonuclear molecules are forbidden. For such cases electronic absorption spectroscopy is the required technique. For reactions in which a heteronuclear diatomic (or a polyatomic) molecule is excited these transitions are allowed. They are overtones of the molecular transitions that occur in the near infrared. These excited products emit spontaneously. The reactions are chemiluminescent, their emission spectra may be obtained and analyzed in order to deduce the detailed course of the reaction. 

Rotational quanta are much smaller than vibrational quanta, and correspond to electromagnetic radiation in the microwave region, typically in the range 103-105MHz (lcm-1 = 3.3 x 104 MHz). Rotational transitions can be excited directly, in microwave absorption spectroscopy (pure rotational spectroscopy), but can also be observed in the rotational fine structure in high-resolution vibrational or electronic spectra. 

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