Molecular rotational resonance method

The alkali halide molecules have been studied comprehensively by molecular beam electric resonance methods. Table 8.14 presents a summary with references. In most cases the electric quadrupole coupling constants have been determined, and usually also the nuclear spin-rotation constants. 

The first successful application of molecular beam electric resonance to the study of a short-lived free radical was achieved by Meerts and Dymanus [142] in their study of OH. They were also able to report spectra of OD, SH and SD. Their electric resonance instrument was conventional except for a specially designed free radical source, in which OH radicals were produced by mixing H atoms, formed from a microwave discharge in H2, with N02 (or H2S in the case of SH radicals). In table 8.24 we present a complete A-doublet data set for OH, including the sets determined by Meerts and Dymanus, with J = 3/2 to 11/2 for the 2n3/2 state, and 1/2 to 9/2 for the 2ni/2 state. Notice that, for the lowest rotational level (7 = 3/2 in 2n3/2), the accuracy of the data is higher. These transitions were observed by ter Meulen and Dymanus [143], not by electric resonance methods, but by beam maser spectroscopy, with the intention of providing particularly accurate data for astronomical purposes. This is the moment for a small diversion into the world of beam maser spectroscopy. It has been applied to a large number of polyatomic molecules, but apparently OH is the only diatomic molecule to be studied by this method. 

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... 

Spectroscopic methods, such as FT-infrared (FTIR) and Raman spectroscopy detect changes in molecular vibrational characteristics in noncrystalline solid and supercooled liquid states. Various nuclear magnetic resonance (NMR) techniques and electron spin resonance (ESR) spectroscopy, however, are more commonly used, detecting transition-related changes in molecular rotation and diffusion (Champion et al. 2000). These methods have been used for studies of the amorphous state of a number of sugars in dehydrated and freeze-concentrated systems (Roudaut et al. 2004). 

Infrared and Raman spectroscopy are important analytical tools used to investigate a wide variety of molecules in the solid, liquid, and gas states, and yielding complementary information about molecular structure and molecular bonds. Both methods supply information about resonances caused by vibration, vibration-rotation, or rotation of the molecular framework, but because the interaction mechanism between radiation and the molecule differs in the two types, the quantum-mechanical selection rules differ as well. Therefore, not all of the molecular motions recorded by one type of spectroscopy will necessarily be recorded by the other. The geometrical configuration of the molecule and the distribution of electrical charge within that configuration determine which molecular motions may appear in each type of spectrum. 

As already mentioned, in some molecular crystals, a hindered or nearly free rotation of entire molecules is observed, e.g. of benzene molecules in crystals of benzene, or of molecular groups, e.g. of CH3 groups in crystals of methyl naphthalene. These motions are stochastic and are termed pseudorotations or reorientations. These two terms denote the two limiting approximations, that of free rotation and that of a fixed orientation of the molecules or molecular groups. Experimental methods which have proved useful for the investigation of these stochastic motions are nuclear-spin magnetic resonance (NMR) [24] and quasielastic neutron scattering [35, 36]. 

The NF radical is isoelectronic with O2 and the three low-lying electronic states in this case have relative energies of 0, 12003.6 and 18 877.05 cm The rotational spectra of all three states have been studied, and we will describe the and A state spectra later in this chapter. Similarly, the SO and NCI radicals are isoelectronic, with the outermost pair of electrons occupying a nZp) molecular orbital, which again gives rise to die tiuee electronic states described above. All three states for both SO and NCI have been studied by pure rotational spectroscopy, and the open shell states have also been investigated by magnetic resonance methods. In this section we concentrate on the rotational spectra of the h states. 

Built-up multilayers can be obtained only for transfer achieved at a surface far beyond the plateau regime, generally around 35 mN/m. Hence the resulting films are just a disordered superposition of oken monocrystals, with a random orientation in the plane of the support, as shown in Fig. 2b. As a consequence, the normal to the support behaves as an axis of full rotation. Such a macroscopic configuration is easy to investigate. This was done by the use of two different resonance methods, namely, linear dichroism and electron spin resonance, with the following result TCNQ radical anions lie completely flat on the substrate in the dimeric form [9]. Obviously, such a structure is not compatible with an in-plane conductivity, for which TCNQ molecular planes should be perpendicular to the substrate. In addition, the complete charge transfer between pyridinium and TCNQ prevents any kind of electron conductivity in the film and, as expected, the electrical properties of the pristine film are those of an insulator. 

The nuclear resonant inelastic and quasi-elastic scattering method has distinct features favorable for studies concerning the microscopic dynamics (i.e., lattice vibration, diffusion, and molecular rotation) of materials. One advantageous feature is the ability to measure the element-specific dynamics of condensed matter. For example, in solids the partial phonon density of states can be measured. Furthermore, measurements under exotic conditions -such as high pressure, small samples, and thin films - are possible because of the high brilliance of synchrotron radiation. (For the definition of brilliance, see O Sect. 50.3.4.5 of Chap. 50, Vol. 5, on Particle Accelerators. ) This method is applicable not only to solids but also to liquids and gases, and there is no limitation concerning the sample temperature. 

Table 2. Absolute Shielding Scales Based on Measured Spin-Rotation Constants (Method 3 in the Text) from Molecular Beam Magnetic/Electric Resonance or High-Resolution Microwave Spectroscopy...

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