Semiclassical Description

Dispersion forces caimot be explained classically but a semiclassical description is possible. Consider the electronic charge cloud of an atom to be the time average of the motion of its electrons around the nucleus. 

Sun X, Wang H and Miller W H 1998 Qn the semiclassical description of quantum coherence in thermal rate constants J. Chem. Phys. 109 4190... 

Stock G and Thoss M 1997 Semiclassical description of nonadiabatic quantum dynamics Phys. Rev. Lett. 78 578... 

Fig. 5.1. The semiclassical description of angular momentum distribution relaxation (a) and rotational energy relaxation at Ea — 0 (6).

FIGURE 2.2 Bohr s semiclassical description of stopping power in terms of the impact parameter. The coulomb interaction is taken at its peak value over the track segment AOB and zero outside. 

Due to the development of efficient initial-value representations of the semiclassical propagator, recently there has been considerable progress in the semiclassical description of multidimensional quantum processes [104—111,... 

Considering the semiclassical description of nonadiabatic dynamics, only the mapping approach [99, 100] and the equivalent formulation that is obtained by requantizing the classical electron analog model of Meyer and Miller [112] appear to be amenable to a numerical treatment via an initial-value representation [114, 116, 117, 121, 122]. Other semiclassical formulations such as Pechukas path-integral formulation [45] and the various connection... 

Second, the mapping approach to nonadiabatic quantum dynamics is reviewed in Sections VI-VII. Based on an exact quantum-mechanical formulation, this approach allows us in several aspects to go beyond the scope of standard mixed quantum-classical methods. In particular, we study the classical phase space of a nonadiabatic system (including the discussion of vibronic periodic orbits) and the semiclassical description of nonadiabatic quantum mechanics via initial-value representations of the semiclassical propagator. The semiclassical spin-coherent state method and its close relation to the mapping approach is discussed in Section IX. Section X summarizes our results and concludes with some general remarks. 

A semiclassical description is well established when both the Hamilton operator of the system and the quantity to be calculated have a well-defined classical analog. For example, there exist several semiclassical methods for calculating the vibrational autocorrelation function on a single excited electronic surface, the Fourier transform of which yields the Franck-Condon spectmm [108, 109, 150, 244]. In particular, semiclassical methods based on the initial-value representation of the semiclassical propagator [104-111, 245-248], which circumvent the cumbersome root-search problem in boundary-value-based semiclassical methods, have been successfully applied to a variety of systems (see, for example, Refs. 110, 111, 161, and 249 and references therein). The mapping procedure introduced in Section VI results in a quantum-mechanical Hamiltonian with a well-defined classical limit, and therefore it... 

Table 1 Values of the atomic electron density at the nucleus, p(0) evaluated with the present modified TFD method compared to HF values by means of the percent deviation (%). Also, the values of 2 Z tq are displayed where tq is the switching point among the quantum mechanical and the semiclassical description (see text).

The highly excited and reactive dynamics, the details of which have been made accessible by recently developed experimental techniques, are characterized by transitions between classically regular and chaotic regimes. Now molecular spectroscopy has traditionally relied on perturbation expansions to characterize molecular energy spectra, but such expansions may not be valid if the corresponding classical dynamics turns out to be chaotic. This leads us to a reconsideration of such perturbation techniques and provides the starting point for our discussion. From there, we will proceed to discuss the Gutzwiller trace formula, which provides a semiclassical description of classically chaotic systems. 

The basis for the semiclassical description of kinetics is the existence of two well separated time scales, one of which describes a slow classical evolution of the system and the other describes fast quantum processes. For example, the collision integral in the Boltzmann equation may be written as local in time because quantum-mechanical scattering is assumed to be fast as compared to the evolution of the distribution function. 

Since his arrival at McMaster in 1988, Randall Dumont has focused on statistical theories and their origin in quantum and classical mechanics. His interests include the development of Monte Carlo implementations of statistical theory wherein dynamical processes are simulated by random walks on potential energy surfaces. The breakdown of statistical theory and the appearance of nonexponential population decay are also topics of his ongoing investigations. Other questions of interest are the incorporation of quantum effects into statistical theory and the effects of collisions on reaction processes. He has a special interest in argon cluster evaporation in vacuum197 and in the description of simple isomerization reactions.198 His other interests include the semiclassical description of classically unallowed processes such as tunneling.199... 

M. Thoss and G. Stock. Mapping approach to the semiclassical description of nonadiabatic quantum dynamics. Phys. Rev. A, 59(l) 64-79, Jan 1999. 

Miller, W.H. (1985). Semiclassical methods in chemical dynamics, in Semiclassical Descriptions of Atomic and Nuclear Collisions, ed. J. Bang and J. de Boer (Elsevier, Amsterdam). 

The second strategy we mention in this rapid survey replaces the QM description of the solvent-solvent and solute-solvent with a semiclassical description. There is a large variety of semiclassical descriptions for the interactions involving solvent molecules, but we limit ourselves to recall the (1,6,12) site formulation, the most diffuse. The interaction is composed of three terms defined in the formula by the inverse power of the corresponding interaction term (1 stays for coulombic interaction, 6 for dispersion and 12 for repulsion). Interactions are allowed for sites belonging to different molecules and are all of two-body character (in other words all the three- and many-body interactions appearing in the cluster expansion of the Hss and HMS terms of the Hamiltonian (1.1)... 

This restriction rules out all discrete models exclusively based on semiempirical force fields, leaving among the discrete models the MC/QM and the MD/QM procedures, in which the second part of the acronyms indicates that the solute is described at the quantum mechanical (QM) level, as well as the full ab initio MD description, and some mixed procedures that derive the position of some solvent molecules from semiclassical simulations, replace the semiclassical description with the QM one, and repeat the calculation on these small supermolecular clusters. The final stage is to perform an average on the results obtained with these clusters. These methods can be used also to describe electronic excitation processes, but at present, their use is limited to simple cases, such as vertical excitations of organic molecules of small or moderate size. This limitation is due to the cost of computations, and there is a progressive trend toward calculations for larger systems. 

The collinear model (Eq. (15)) has been successfully used in the semiclassical description of many bound and resonant states in the quantum mechanical spectrum of real helium [49-52] and plays an important role for the study of states of real helium in which both electrons are close to the continuum threshold [53, 54]. The quantum mechanical version of the spherical or s-wave model (Eq. (16)) describes the Isns bound states of real helium quite well [55]. The energy dependence of experimental total cross sections for electron impact ionization is reproduced qualitatively in the classical version of the s-wave model [56] and surprisingly well quantitatively in a quantum mechanical calculation [57]. The s-wave model is less realistic close to the break-up threshold = 0, where motion along the Wannier ridge, = T2, is important. 

The models for the control processes start with the Schrodinger equation for the molecule in interaction with a laser field that is treated either as a classical or as a quantized electromagnetic field. In Section II we describe the Floquet formalism, and we show how it can be used to establish the relation between the semiclassical model and a quantized representation that allows us to describe explicitly the exchange of photons. The molecule in interaction with the photon field is described by a time-independent Floquet Hamiltonian, which is essentially equivalent to the time-dependent semiclassical Hamiltonian. The analysis of the effect of the coupling with the field can thus be done by methods of stationary perturbation theory, instead of the time-dependent one used in the semiclassical description. In Section III we describe an approach to perturbation theory that is based on applying unitary transformations that simplify the problem. The method is an iterative construction of unitary transformations that reduce the size of the coupling terms. This procedure allows us to detect in a simple way dynamical or field induced resonances—that is, resonances that... 

X. Sun, H. B. Wang, and W. H. Miller (1998) On the semiclassical description of quantum coherence in thermal rate constants. J. Chem,. Phys. 109, p. 4190 X. Sun, H. B. Wang, and W. H. Miller (1998) Semiclassical theory of electronically nonadaibatic molecular dynamics Results of a linearized approximation to the initial value representation. J. Chem. Phys. 109, p. 7064... 

With a semiclassical description such as this it is possible to discuss rainbow phenomena53 in a manner parallel to the treatment in elastic scattering.5,6 Doll49 has also discussed the quenching of the diffraction spots which results when imperfect periodicities of the lattice are taken into account. 

One has at hand, therefore, a completely general semiclassical mechanics which allows one to construct the classical-limit approximation to any quantum mechanical quantity, incorporating the complete classical dynamics with the quantum principle of superposition. As has been emphasized, and illustrated by a number of examples in this review, all quantum effects— interference, tunnelling, resonances, selection rules, diffraction laws, even quantization itself—arise from the superposition of probability amplitudes and are thus contained at least qualitatively within the semiclassical description. The semiclassical picture thus affords a broad understanding and clear insight into the nature of quantum effects in molecular dynamics. 

Many of the available computations on radicals are strictly applicable only to the gas phase they do not account for any medium effects on the molecules being studied. However, in many cases, medium effects cannot be ignored. The solvated electron, for instance, is all medium effect. The principal frameworks for incorporating the molecular environment into quantum chemistry either place the molecule of interest within a small cluster of substrate molecules and compute the entire cluster quantum mechanically, or describe the central molecule quantum mechanically but add to the Hamiltonian a potential that provides a semiclassical description of the effects of the environment. The 1975 study by Newton (28) of the hydrated and ammoniated electron is the classic example of merging these two frameworks Hartree-Fock wavefunctions were used to describe the solvated electron together with all the electrons of the first solvent shell, while more distant solvent molecules were represented by a dielectric continuum. The intervening quarter century has seen considerable refinement in both quantum chemical techniques and dielectric continuum methods relative to Newton s seminal work, but many of his basic conclusions... 

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