Mechanical harmonic oscillator analyses

One of most popular techniques for dynamic mechanical analysis is the torsion pendulum method. In a modification of this method designed to follow curing processes, a torsion bar is manufactured from a braid of fibers impregnated with the composition to be studied this is the so-called torsional braid analysis (TBA) method.61 62,148 The forced harmonic oscillation method has been also used and has proven to be valuable. This method employs various types of rheogoniometers and vibroreometers,1 9,150 which measure the absolute values of the viscoelastic properties of the system under study these properties can be measured at any stage of the process. The use of computers further contributes to improvements in dynamic mechanical analysis methods for rheokinetic measurements. As will be seen below, new possibilities are opened up by applying computer methods to results of dynamic measurements. 

Statistical Mechanics of the Harmonic Oscillator. As has already been argued in this chapter, the harmonic oscillator often serves as the basis for the construction of various phenomena in materials. For example, it will serve as the basis for our analysis of vibrations in solids, and, in turn, of our analysis of the vibrational entropy which will be seen to dictate the onset of certain structural phase transformations in solids. We will also see that the harmonic oscillator provides the foundation for consideration of the jumps between adjacent sites that are the microscopic basis of the process of diffusion. 

Until now, our treatment has been built in exactly the same terms that might have been used in work on normal modes of vibration in the latter part of the nineteenth century. However, it is incumbent upon us to revisit these same ideas within the quantum mechanical setting. The starting point of our analysis is the observation embodied in eqn (5.19), namely, that our harmonic Hamiltonian admits of a decomposition into a series of independent one-dimensional harmonic oscillators. We may build upon this observation by treating each and every such oscillator on the basis of the quantum mechanics discussed in chap. 3. In light of this observation, for example, we may write the total energy of the harmonic solid as... 

Balmer s formula, but- also to establish one of the most important results of quantum mechanics the quantization of angular momentum in units of A/2tt. This result arises from the analysis in his paper it is not his starting point. Bohr s quantum postulate was based on Planck s assumption of the quantization of the energy of harmonic oscillators. By analogy with this, and arguing from a correspondence with classical physics, he set a restrictive condition on the mechanically possible electron orbits, and postulated that this limited set of orbits should be non-radiating. 

Thermodynamic properties calculated for the current study are presented in Table 7.5. Enthalpy of formation and entropy values are reported at 298 K, as most experimental data are referenced or available at 298 K. This facilitates the use of these thermodynamic properties and the use of isodesmic reaction set. Entropies and heat capacities are calculated by statistical mechanics using the harmonic-oscillator approximation for vibrations, based on frequencies and moments of inertia of the optimized B3LYP/6-311G(d,p) structures. Torsional frequencies are not included in the contributions to entropy and heat capacities instead, they are replaced with values from a separate analysis on each internal rotor analysis (IR). 

The quantum mechanical information that follows from a normal mode analysis must reveal the same mechanical equivalence to a set of disconnected oscillators as the classical analysis. Each such oscillator (normal mode of vibration) can exist in any of the states possible for a one-dimensional harmonic oscillator. Each has its own contribution to the energy of the system, and thus, the Hamiltonian in Equation 7.35 corresponds to a quantum mechanical energy level expression... 

Comparisons of the correlation functions calculated quantum mechanically and semiclassically, like those presented in Fig. 6.2, show that the correction due to the dipole moment gradient included in (6.34) sometimes improves the accuracy especially for short propagation times. This correction affects not only the amplitude of the correlation function oscillation, but also its frequency and distortions due to the presence of high harmonics in the spectrum. An analysis of the spectrum of the correlation function indicates that including this correction in the formula enables additional quantum effects to be taken into account. 

Molecular spectroscopy is now a mature field of study. It is, however, difficult to find references superior to the classic treatise written by Herzberg nearly 50 years ago (1). The origin of vibrational spectra is usually considered in terms of mechanical oscillations associated with mass of the nuclei and interconnecting springs (9). Vibrational spectroscopy considers the frequency, shape, and intensity of internuclear motions due to incident electromagnetic fields. In the harmonic approximation, the vibrational bands are associated with transitions between nearest vibrational states. When higher order transitions, resonance, and coupling between vibrational motions require analysis, quantum mechanical treatment is mandated (1). Improvements and advancements in poljuner spectroscopy are driven by the many problems of interest in the polymer community. 

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