Rotational vibrating system

Resonant vibration. Any of the forced vibration loads, such as cyclic or misalignment loads, may have a frequency that coincides with a natural frequency of the rotating-shaft system, or any component of the complete power plant and its foundation, and may, thus, excite vibration resonance. 

One possibility for this was demonstrated in Chapter 3. If impact theory is still valid in a moderately dense fluid where non-model stochastic perturbation theory has been already found applicable, then evidently the continuation of the theory to liquid densities is justified. This simplest opportunity of unified description of nitrogen isotropic Q-branch from rarefied gas to liquid is validated due to the small enough frequency scale of rotation-vibration interaction. The frequency scales corresponding to IR and anisotropic Raman spectra are much larger. So the common applicability region for perturbation and impact theories hardly exists. The analysis of numerous experimental data proves that in simple (non-associated) systems there are three different scenarios of linear rotator spectral transformation. The IR spectrum in rarefied gas is a P-R doublet with either resolved or unresolved rotational structure. In the process of condensation the following may happen. 

The function g is the partition function for the transition state, and Qr is the product of the partition functions for the reactant molecules. The partition function essentially counts the number of ways that thermal energy can be stored in the various modes (translation, rotation, vibration, etc.) of a system of molecules, and is directly related to the number of quantum states available at each energy. This is related to the freedom of motion in the various modes. From equations 6.5-7 and -16, we see that the entropy change is related to the ratio of the partition functions ... 

As a consequence of the transformation, the equation of motion depends on three extra coordinates which describe the orientation in space of the rotating local system. Furthermore, there are additional terms in the Hamiltonian which represent uncoupled momenta of the nuclear and electronic motion and moment of inertia of the molecule. In general, the Hamiltonian has a structure which allows for separation of electronic and vibrational motions. The separation of rotations however is not obvious. Following the standard scheme of the various contributions to the energy, one may assume that the momentum and angular momentum of internal motions vanish. Thus, the Hamiltonian is simplified to the following form. 

Not all of these induced dipole types may exist in any given system. The components that exist generally couple in different ways to the translational, rotational, vibrational, etc., states of the complex and usually are associated with different selection rules, thus generating different parts of the collision-induced spectra. 

If collisional systems involving one or more molecules are considered, the internal degrees of freedom of the molecule(s) (e.g., rotation, vibration) have to be taken into account. This often leads to cumbersome notations and other complications. Furthermore, we now have to deal with anisotropic intermolecular interactions which again calls for a significant modification of the formal theory. In that sense, this Chapter differs from the previous one but otherwise the reader will find here much the same material, techniques, etc., as discussed in Chapter 5. 

When the total energy of a system is the sum of the energies from the different degrees of freedom, for example, translation, rotation, vibration, and electronic, then the partition function for a combination of the energy levels is the product of the partition functions for each type. Thus,... 

To study the reaction of molecules on surfaces in detail, it is important to consider the different degrees of freedom the system has. The reacting molecule s rotational, vibrational and translational degrees of freedom will affect its interaction as it hits the surface. In addition, the surface has lattice vibrations (phonons) and electronic degrees of freedom. Both the lattice vibrations and the electrons can act as efficient energy absorbers or energy sources in a chemical reaction. 

In order to discuss the spectroscopic properties of diatomic molecules it is useful to transform the kinetic energy operators (2.5) or (2.6) so that the translational, rotational, vibrational, and electronic motions are separated, or at least partly separated. In this section we shall discuss transformations of the origin of the space-fixed axis system the following choices of origin have been discussed by various authors (see figure 2.1) ... 

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