Dynamical rules simplifications

The polarization dependence of the photon absorbance in metal surface systems also brings about the so-called surface selection rule, which states that only vibrational modes with dynamic moments having components perpendicular to the surface plane can be detected by RAIRS [22, 23 and 24]. This rule may in some instances limit the usefidness of the reflection tecluiique for adsorbate identification because of the reduction in the number of modes visible in the IR spectra, but more often becomes an advantage thanks to the simplification of the data. Furthenuore, the relative intensities of different vibrational modes can be used to estimate the orientation of the surface moieties. This has been particularly useful in the study of self-... 

An even more drastic simplification of the dynamics is made in lattice-gas automaton models for fluid flow [127,128]. Here particles are placed on a suitable regular lattice so that particle positions are discrete variables. Particle velocities are also made discrete. Simple rules move particles from site to site and change discrete velocities in a manner that satisfies the basic conservation laws. Because the lattice geometry destroys isotropy, artifacts appear in the hydrodynamics equations that have limited the utility of this method. Lattice-gas automaton models have been extended to treat reaction-diffusion systems [129]. 

The last item concerns not only space and time discretization but also drastic simplification of the collision operator and particle motion rules as well, e.g., by employing cellular automata, lattice gas models [37,38], or stochastic models such as stochastic rotation dynamics [39]. 

Fundamental simplifications of particle-particle colhsion operator and particle-motion rules, result in the on-grid cellular automata models of fluid dynamics, i.e., LG and LBG schemes. LG hydrodynamics [37,38] describes the approach to fluid dynamics using a microworld constructed as an automaton universe, where the microscopic dynamics is not on the basis of a description of... 

On the other hand, the LBG method can capture both mesoscopic and macroscopic scales even larger than those that can be modeled by discrete-particle methods. This advantage is due to computational simplicity of the method, which comes from coarse-grained discretization of both the space and time and drastic simplification of collision rules between particles. We can look at the validity of these simplifications by comparing them with more realistic discrete-particles simulation. We regard both DPD and LBG as being complementary computational tools for modeling the slow dynamics in porous media over wide spatio-temporal scales. 

The results presented in this chapter show that the use of proper effective models, in combination with calculations based on the exact vibrational Hamiltonian, constitutes a promising approach to study the laser driven vibrational dynamics of polyatomic molecules. In this context, the MCTDH method is an invaluable tool as it allows to compute the laser driven dynamics of polyatomic molecules with a high accuracy. However, our models still contain simplifications that prevent a direct comparison of our results with potential experiments. First, the rotational motion of the molecule was not explicitly described in the present work. The inclusion of the rotation in the description of the dynamics of the molecule is expected to be important in several ways. First, even at low energies, the inclusion of the rotational structure would result in a more complicated system with different selection rules. In addition, the orientation of the molecule with respect to the laser field polarization would make the control less efficient because of the rotational averaging of the laser-molecule interaction and the possible existence of competing processes. On the other hand, the combination of the laser control of the molecular alignment/orientation with the vibrational control proposed in this work could allow for a more complete control of the dynamics of the molecule. A second simplification of our models concerns the initial state chosen for the simulations. We have considered a molecule in a localized coherent superposition of vibrational eigenstates but we have not studied the preparation of this state. We note here that a control scheme for the localiza-... 

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