Rotational levels spectrometer

While a laser beam can be used for traditional absorption spectroscopy by measuring / and 7q, the strength of laser spectroscopy lies in more specialized experiments which often do not lend themselves to such measurements. Other techniques are connnonly used to detect the absorption of light from the laser beam. A coimnon one is to observe fluorescence excited by the laser. The total fluorescence produced is nonnally proportional to the amount of light absorbed. It can be used as a measurement of concentration to detect species present in extremely small amounts. Or a measurement of the fluorescence intensity as the laser frequency is scaimed can give an absorption spectrum. This may allow much higher resolution than is easily obtained with a traditional absorption spectrometer. In other experiments the fluorescence may be dispersed and its spectrum detennined with a traditional spectrometer. In suitable cases this could be the emission from a single electronic-vibrational-rotational level of a molecule and the experimenter can study how the spectrum varies with level. 

Figure 10.33. Tandem mass spectrometer system employing electric field dissociation, designed to enable the study of microwave spectra of molecular ions involving vibration-rotation levels lying close to the dissociation limit.

J = 3/2, 5/2 and 7/2 levels of both fine-structure states. Also shown are the /l-doublet transitions observed, first by Dousmanis, Sanders and Townes [4], and subsequently by ter Meulen and Dymanus [165] andMeertsandDymanus [166]. The later studies [166] used molecular beam electric resonance methods which were described in chapter 8, and the most accurate laboratory measurements of transitions within the lowest rotational level were those of ter Meulen and Dymanus [165] using a beam maser spectrometer, also described in chapter 8. In the years following these field-free experiments, attention... 

Rotational features of almost aU H-bonded complexes in the gaseous phase appear in the microwave region, with wavenumbers less than 10 cm They correspond to transitions between pure rotational levels, pure meaning that vibrations remain unchanged, or no vibrational transition accompanies such rotational transitions. Rotational features, however, also appear in the IR spectra of these H-bonded complexes. IR bands correspond to transitions between various vibrational levels of a molecule. When this molecule is isolated, as in the gas phase, these transitions are always accompanied by transitions between rotational levels that obey the same selection rules as pure rotational transitions detected in microwave spectroscopy. The information conveyed by these rotational features in IR spectra are therefore most similar to those conveyed by microwave spectra, even if the mechanism at the origin of their appearance is different. Their interests lie in the use of an IR spectrometer, a common instrument in many laboratories, instead of a microwave spectrometer, which is a much more specialized instrament. However, the resolution of usual IR spectrometers are lower than that of microwave spectrometers that use Fabry-Perot cavities. This IR technique has been used in the case of simple H-bonded dimers with relatively small moments of inertia, such as, for instance, F-H- -N C-H (3). Such complexes are far from simple to manipulate, but provide particularly simple IR spectra with a limited number of bands that do not show any overlap. 

The fundamental absorption band of PH in its ground state X was observed at high resolution using a tunable diode laser spectrometer eighteen lines betwen 2224.4125 and 2107.8160 cm" (4.50 to 4.74 pm) have been identified as P-branch transitions with N" = 3 to 7 and 9, where each transition exhibits the fine-structure triplet splitting due to AJ = AN transitions between the three sublevels (J = N +1, N, N -1) of the respective rotational levels N" and N. Two further lines at 2292.1918 and 2308.1542 cm" (-4.3 pm) have been identified as the R-branch transitions with N", J " = 0,1 and 1,0. Hyperfine splitting could not be resolved. The analysis, which included rotational and centrifugal distortion effects as well as spin-spin... 

Inversion Splitting. The inversion splitting Aj of PH3 in the vibrational ground state is extremely small and all efforts to detect it by direct measurement failed [24 to 26]. An attempt to measure Aj with a molecular-beam electric-resonance spectrometer revealed that the inversion splitting must be lower than the resolution of the spectrometer (1 kHz) [26]. Similarly, from a high-resolution IR study of the 4v2 band of PH3 followed Aj< 0.02 cm" [25]. Much lower upper limits of A < 0.6(801) Hz [27], 3.8(400) Hz [28], and 8.4(418) Hz [29] were obtained from an evaluation of the modulation of the K splitting of rotational levels by the inversion contribution. 

Two new bands — in-phase (ui) and out-of-phase (I ls) antisymmetric CH2 stretching vibrations of allyl radical have been obtained in the slit jet discharge spectrometer, as the sample spectra shown in the top panel of Fig. 5.18. The data have been successfully analyzed with a Watson asymmetric rotor Hamiltonian, yielding precise band origins and rotational constants for both bands. The high quality of least squares fits to ground state combination differences indicates that the rotational level structure in the lower state is well behaved, while the reduced quality of fits to the vibrational transitions, on the other hand, suggest the presence of Coriolis mediated rotational perturbations in the upper state. Due to sub-Doppler resolution (Ai/ 70 MHz) in the slit jet expansion. 

---