Degrees of freedom dynamics

The methods and procedures for blast resistant design can vary considerably in complexity, accuracy, cost and efficiency from simple conventional static design approach to complex transient nonlinear, multi-degree of freedom dynamic design methods. To assist designers in striking a balance amongst these, Chapter 6 provides... 

How the correspondence principle should be applied to an atomic system thus depends critically on whether or not there exists a multiperiodic representation of the classical trajectories - the question first raised by Einstein. If the system possesses multiperiodic orbits, then its motion becomes separable, i.e. it becomes equivalent to as many independent modes as there are degrees of freedom. Dynamical separability is assumed in all independent particle and perturbative models of the many-electron atom. It is, however, not strictly applicable and the successes of simple quantum theory for many-electron systems are, to say the least, surprising. It was pointed out by Einstein, who based his arguments on the work of Poincare [519], that there exists no true separation of the three-body problem. 

Chapter 3 presented the Bayesian spectral density approach for the parametric identification of the multi-degree-of-freedom dynamical model using the measured response time history. The methodology is applicable for linear models and can also be utilized for weakly nonlinear models by obtaining the mean spectrum with equivalent linearization or strongly nonlinear models by obtaining the mean spectrum with simulations. The stationarity assumption in modal/model identification for an ambient vibration survey is common but there are many cases where the response measurements are better modeled as nonstationary, e.g., the structural response due to a series of wind gusts or seismic responses. In the literature, there are very few approaches which consider explicitly nonstationary response data, for example, [226,229]. Meanwhile, extension of the Bayesian spectral density approach for nonstationary response measurement is difficult since construction of the likelihood function is nontrivial in the frequency domain. Estimation of the time-dependent spectrum requires a number of data sets, which are associated with the same statistical time-frequency properties but this is impossible to achieve in practice. 

Experiments and theoretical models discussed in this review are restricted to single, isolated vesicles in thermodynamic equilibrium with respect to their morphological degrees of freedom. Dynamical aspects and the physics of vesicle adhesion are covered in Chapter 7. Giant vesicles are generally not in thermo-... 

In a molecular system with internal degrees of freedom, dynamic storage of energy, which leads to a frequency dependent absorption of sound, occurs, through inelastic collisions. The dispersion associated with a simple rotational isomeric process may be described by the equation... 

For very fast reactions, as they are accessible to investigation by pico- and femtosecond laser spectroscopy, the separation of time scales into slow motion along the reaction path and fast relaxation of other degrees of freedom in most cases is no longer possible and it is necessary to consider dynamical models, which are not the topic of this section. But often the temperature, solvent or pressure dependence of reaction rate... 

Straub J E, Borkovec M and Berne B J 1987 On the calculation of dynamical friction on intramolecular degrees of freedom J. Phys. Chem. 91 4995... 

The direct dissociation of diatomic molecules is the most well studied process in gas-surface dynamics, the one for which the combination of surface science and molecular beam teclmiques allied to the computation of total energies and detailed and painstaking solution of the molecular dynamics has been most successful. The result is a substantial body of knowledge concerning the importance of the various degrees of freedom (e.g. molecular rotation) to the reaction dynamics, the details of which are contained in a number of review articles [2, 36, 37, 38, 39, 40 and 41]. 

The fomialism outlined in the previous sections is very usefiil for small systems, but is, as explained, impractical for more than six to ten strongly interacting degrees of freedom. Thus, alternate approaches are required to represent dynamics for large systems. Currently, there are many new approaches developed and tested for this purpose, and these approaches are broadly classified as follows ... 

Often a degree of freedom moves very slowly for example, a heavy-atom coordinate. In that case, a plausible approach is to use a sudden approximation, i.e. fix that coordinate and do reduced dimensionality quantum-dynamics simulations on the remaining coordinates. A connnon application of this teclmique, in a three-dimensional case, is to fix the angle of approach to the target [120. 121] (see figure B3.4.14). 

Molecular dynamics tracks tire temporal evolution of a microscopic model system tlirough numerical integration of tire equations of motion for tire degrees of freedom considered. The main asset of molecular dynamics is tliat it provides directly a wealtli of detailed infonnation on dynamical processes. 

Figure C3.2.12. Experimentally observed electron transfer time in psec (squares) and theoretical electron transfer times (survival times, Tau a and Tau b) predicted by an extended Sumi-Marcus model. For fast solvents tire survival times are a strong Emction of tire characteristic solvent relaxation dynamics. For slower solvents tire electron transfer occurs tlirough tire motion of intramolecular degrees of freedom. From [451.

Unlike classical systems in which the Lagrangean is quadratic in the time derivatives of the degrees of freedom, the Lagrangeans of both quantum and fluid dynamics are linear in the time derivatives of the degrees of freedom. 

Election nuclear dynamics theory is a direct nonadiababc dynamics approach to molecular processes and uses an electi onic basis of atomic orbitals attached to dynamical centers, whose positions and momenta are dynamical variables. Although computationally intensive, this approach is general and has a systematic hierarchy of approximations when applied in an ab initio fashion. It can also be applied with semiempirical treatment of electronic degrees of freedom [4]. It is important to recognize that the reactants in this approach are not forced to follow a certain reaction path but for a given set of initial conditions the entire system evolves in time in a completely dynamical manner dictated by the inteiparbcle interactions. 

The time dependence of the molecular wave function is carried by the wave function parameters, which assume the role of dynamical variables [19,20]. Therefore the choice of parameterization of the wave functions for electronic and nuclear degrees of freedom becomes important. Parameter sets that exhibit continuity and nonredundancy are sought and in this connection the theory of generalized coherent states has proven useful [21]. Typical parameters include molecular orbital coefficients, expansion coefficients of a multiconfigurational wave function, and average nuclear positions and momenta. We write... 

If the PES are known, the time-dependent Schrbdinger equation, Eq. (1), can in principle be solved directly using what are termed wavepacket dynamics [15-18]. Here, a time-independent basis set expansion is used to represent the wavepacket and the Hamiltonian. The evolution is then carried by the expansion coefficients. While providing a complete description of the system dynamics, these methods are restricted to the study of typically 3-6 degrees of freedom. Even the highly efficient multiconfiguration time-dependent Hartree (MCTDH) method [19,20], which uses a time-dependent basis set expansion, can handle no more than 30 degrees of freedom. 

Full quantum wavepacket studies on large molecules are impossible. This is not only due to the scaling of the method (exponential with the number of degrees of freedom), but also due to the difficulties of obtaining accurate functions of the coupled PES, which are required as analytic functions. Direct dynamics studies of photochemical systems bypass this latter problem by calculating the PES on-the-fly as it is required, and only where it is required. This is an exciting new field, which requires a synthesis of two existing branches of theoretical chemistry—electronic structure theory (quantum chemistiy) and mixed nuclear dynamics methods (quantum-semiclassical). 

Solving the Eqs. (C.6-C.8,C.12,C.13) comprise what is known as the Ehrenfest dynamics method. This method has appealed under a number of names and derivations in the literatnre such as the classical path method, eilconal approximation, and hemiquantal dynamics. It has also been put to a number of different applications, often using an analytic PES for the electronic degrees of freedom, but splitting the nuclear degrees of freedom into quantum and classical parts. 

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