Forced oscillator model

Since DFT calculations are in principle only applicable for the electronic ground state, they cannot be used in order to describe electronic excitations. Still it is possible to treat electronic exciations from first principles by either using quantum chemistry methods [114] or time-dependent density-functional theory (TDDFT) [115,116], First attempts have been done in order to calculate the chemicurrent created by an atom incident on a metal surface based on time-dependent density functional theory [117, 118]. In this approach, three independent steps are preformed. First, a conventional Kohn-Sham DFT calculation is performed in order to evaluate the ground state potential energy surface. Then, the resulting Kohn-Sham states are used in the framework of time-dependent DFT in order to obtain a position dependent friction coefficient. Finally, this friction coefficient is used in a forced oscillator model in which the probability density of electron-hole pair excitations caused by the classical motion of the incident atom is estimated. 

Gray, S.K. (1987) A periodically forced oscillator model of van der Waals fiagmentation Classical and quantum dynamics, J.Cfien/.Pfivs- 87, 2051-2061. 

It is now relatively straightforward to extend this forced oscillator model for a single oscillator to the situation in a solid where we have a distribution of oscillators. Omitting the zero-point energy of the crystal we can write the total hamiltonian as... 

In the forced-oscillator model of energy transfer, one has to calculate the force exerted on the target by the colliding projectile. The MO-calculated energy gradient (force) can be used directly in this model. Such a study for the energy transfer in Li + CO2 has recently been carried out. ... 

While the Lorentz model only allows for a restoring force that is linear in the displacement of an electron from its equilibrium position, the anliannonic oscillator model includes the more general case of a force that varies in a nonlinear fashion with displacement. This is relevant when tire displacement of the electron becomes significant under strong drivmg fields, the regime of nonlinear optics. Treating this problem in one dimension, we may write an appropriate classical equation of motion for the displacement, v, of the electron from equilibrium as... 

How relevant are these phenomena First, many oscillating reactions exist and play an important role in living matter. Biochemical oscillations and also the inorganic oscillatory Belousov-Zhabotinsky system are very complex reaction networks. Oscillating surface reactions though are much simpler and so offer convenient model systems to investigate the realm of non-equilibrium reactions on a fundamental level. Secondly, as mentioned above, the conditions under which nonlinear effects such as those caused by autocatalytic steps lead to uncontrollable situations, which should be avoided in practice. Hence, some knowledge about the subject is desired. Finally, the application of forced oscillations in some reactions may lead to better performance in favorable situations for example, when a catalytic system alternates between conditions where the catalyst deactivates due to carbon deposition and conditions where this deposit is reacted away. 

Summary. In this chapter the control problem of output tracking with disturbance rejection of chemical reactors operating under forced oscillations subjected to load disturbances and parameter uncertainty is addressed. An error feedback nonlinear control law which relies on the existence of an internal model of the exosystem that generates all the possible steady state inputs for all the admissible values of the system parameters is proposed, to guarantee that the output tracking error is maintained within predefined bounds and ensures at the same time the stability of the closed-loop system. Key theoretical concepts and results are first reviewed with particular emphasis on the development of continuous and discrete control structures for the proposed robust regulator. The role of disturbances and model uncertainty is also discussed. Several numerical examples are presented to illustrate the results. 

Zero-point energies are obtained from vibrational spectra using experimental frequencies whenever available, while the inactive frequencies are extracted from data calculated by means of an appropriate force-held model. In the harmonic oscillator approximation, the zero-point energy is... 

McKarnin, M. A., Schmidt, L. D., and Aris, R. (1988). Forced oscillations of a self-oscillating bimolecular surface reaction model. Proc. R. Soc., A417, 363-88. 

The harmonic oscillator model does not take into account the real nature of chemical bonds, which are not perfect springs. The force constant k decreases if the atoms are pulled apart and increases significantly if they are pushed close together. The vibrational levels, instead of being represented by a parabolic function as in equation (10.3), are contained in an envelope. This envelope can be described by the Morse equation (Fig. 10.5) ... 

Cohen, R.E., Tschoegl,N.W, Dynamic mechanical properties of block copolymer blends—a study of the effects of terminal chains in elastomeric materials. I. Torsion pendulum measurements. Intern. J, Polymeric Mater. 2, 49-69 (1972) II. Forced oscillation measurements. Ibid 2, 205-223 (1973) III. A mechanical model for entanglement slippage. Ibid (in press). 

A comparative study was done by Kevrekidis and published as I. G. Kevrekidis, L. D. Schmidt, and R. Aris. Some common features of periodically forced reacting systems. Chem. Eng. Sci. 41,1263-1276 (1986). See also two papers by the same authors Resonance in periodically forced processes Chem. Eng. Sci. 41, 905-911 (1986) The stirred tank forced. Chem. Eng. Sci. 41,1549-1560 (1986). A full study of the Schmidt-Takoudis vacant site mechanism is to be found in M. A. McKamin, L. D. Schmidt, and R. Aris. Autonomous bifurcations of a simple bimolecular surface-reaction model. Proc. R. Soc. Lond. A 415,363-387 (1988) Forced oscillations of a self-oscillating bimolecular surface reaction model. Proc. R. Soc. Lond. A 415,363-388 (1988). 

L. Forced Oscillations of a Self-Oscillating Bimolecular Surface Reaction Model... 

FORCED OSCILLATIONS OF A SELF-OSCILLATING BIMOLECULAR SURFACE REACTION MODEL... 

The effects of forced oscillations in the partial pressure of a reactant is studied in a simple isothermal, bimolecular surface reaction model in which two vacant sites are required for reaction. The forced oscillations are conducted in a region of parameter space where an autonomous limit cycle is observed, and the response of the system is characterized with the aid of the stroboscopic map where a two-parameter bifurcation diagram for the map is constructed by using the amplitude and frequency of the forcing as bifurcation parameters. The various responses include subharmonic, quasi-peri-odic, and chaotic solutions. In addition, bistability between one or more of these responses has been observed. Bifurcation features of the stroboscopic map for this system include folds in the sides of some resonance horns, period doubling, Hopf bifurcations including hard resonances, homoclinic tangles, and several different codimension-two bifurcations. 

The model that will be used for forced oscillation studies is one which was first proposed by Takoudis et al. (1981) as a simple example of an isothermal surface reaction without coverage dependent parameters in which limit cycles can occur. The bimolecular reaction between species A and B is presumed to occur as a Langmuir-Hinshelwood bimolecular process except that two adjacent vacant sites on the surface are required for the reaction to take place. 

In figure 2b, there are clearly folds in the left-hand side of the 3/2 and 2/1 resonance horns. This phenomenon had not (when we observed it) been seen in other forced oscillators such as the Brusselator model (Kai Tomita 1979) and the non-isothermal cstr (Kevrekidis et al. 1986), although it may have been missed in previous numerical studies that did not use arc-length continuation. It is however also to be found in unpublished work of Marek s group. The cusp points at M and L are quite different from the apparent cusp ... 

Forced oscillations of a self-oscillating bimo-lecular surface reaction model (with M.A. McKamin and L.D. Schmidt). Proc. Roy. Soc. A417, 363-388 (1988). (Reprint L)... 

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