Classical particles

The miderstanding of molecular motions is necessarily based on quaiitum mechanics, the theory of microscopic physical behaviour worked out in the first quarter of the 20th century. This is because molecules are microscopic systems in which it is impossible—or at least very dangerous —to ignore the dual wave-particle nature of matter first recognized in quaiitum theory by Einstein (in the case of classical waves) and de Broglie (in the case of classical particles). 

First consider one classical particle with energy E = p I(2M). The partition fiinction is... 

H at m energy of 1.2 eV in the center-of-mass frame. By using an atomic orbital basis and a representation of the electronic state of the system in terms of a Thouless determinant and the protons as classical particles, the leading term of the electronic state of the reactants is... 

Techniques have been developed within the CASSCF method to characterize the critical points on the excited-state PES. Analytic first and second derivatives mean that minima and saddle points can be located using traditional energy optimization procedures. More importantly, intersections can also be located using constrained minimization [42,43]. Of particular interest for the mechanism of a reaction is the minimum energy path (MEP), defined as the line followed by a classical particle with zero kinetic energy [44-46]. Such paths can be calculated using intrinsic reaction coordinate (IRC) techniques... 

In this section, the basic theory of molecular dynamics is presented. Starting from the BO approximation to the nuclear Schrddinger equation, the picture of nuclear dynamics is that of an evolving wavepacket. As this picture may be unusual to readers used to thinking about nuclei as classical particles, a few prototypical examples are shown. 

The motivation comes from the early work of Landau [208], Zener [209], and Stueckelberg [210]. The Landau-Zener model is for a classical particle moving on two coupled ID PES. If the diabatic states cross so that the energy gap is linear with time, and the velocity of the particle is constant through the non-adiabatic region, then the probability of changing adiabatic states is... 

This dependency is seen in the Landau-Zener expression for the probability of a classical particle changing states while moving through a non-adiabatic... 

The quantum degrees of freedom are described by a wave function /) = (x, t). It obeys Schrodinger s equation with a parameterized coupling potential V which depends on the location q = q[t) of the classical particles. This location q t) is the solution of a classical Hamiltonian equation of motion in which the time-dependent potential arises from the expectation value of V with regard to tp. For simplicity of notation, we herein restrict the discussion to the case of only two interacting particles. Nevertheless, all the following considerations can be extended to arbitrary many particles or degrees of freedom. 

QCMD describes a coupling of the fast motions of a quantum particle to the slow motions of a classical particle. In order to classify the types of coupled motion we eventually have to deal with, we first analyze the case of an extremely heavy classical particle, i.e., the limit M —> oo or, better, m/M 0. In this adiabatic limit , the classical motion is so slow in comparison with the quantal motion that it cannot induce an excitation of the quantum system. That means, that the populations 6k t) = of the... 

In most real life applications, the evaluation of the forces acting on the classical particles (i.e., the evaluation of the gradient of the interaction potential) is by far the most expensive operation due to the large number of classical degrees of freedom. Therefore we will concentrate on numerical techniques which try to minimize the number of force evaluations. 

Fig. 1. Total energy (in kj/mol) versus time (in fs) for different integrators for a collinear collision of a classical particle with a harmonic quantum oscillator (for details see [2]). Dashed line Nonsymplectic scheme. Dotted Symplectic integrator of first order. Solid PICKABACK (symplectic, second order).

For ease of presentation, we consider the case of just one quantum degree of freedom with spatial coordinate x and mass m and N classical particles with coordinates q e and diagonal mass matrix M e tj Wxsjv Upon... 

Finally, we like to mention that the QCMD model reduces to the Born-Oppenheimer approximation in case the ratio of the mass m of the quantum particles to the masses of the classical particles vanishes [6], This implies... 

The solution to Wi is just a translation of classical particles with constant momentum p. 

The intriguing point about the second set of equations is that q is now kept constant. Thus the vector ip evolves according to a time-dependent Schrddinger equation with time-independent Hamilton operator H[q) and the update of the classical momentum p is obtained by integrating the Hellmann-Feynman forces [3] acting on the classical particles along the computed ip t) (plus a constant update due to the purely classical force field). 

For the system (16) it is known [5] under non-resonance assumptions that in the limit m/M 0 the motion of the classical particle is governed... 

A method is outlined by which it is possible to calculate exactly the behavior of several hundred interacting classical particles. The study of this many-body problem is carried out by an electronic computer which solves numerically the simultaneous equations of motion. The limitations of this numerical scheme are enumerated and the important steps in making the program efficient on the computer are indicated. The applicability of this method to the solution of many problems in both equilibrium and nonequilibrium statistical mechanics is discussed. 

The first thing to note is that the nuclei are very much more massive than the electron (by a factor of 1836). If they were classical particles, we might argue that their velocities would be very much less than the velocity of the electron, and so to a first approximation the motion of the electron should be the same as if the nuclei were fixed in space. 

An intrinsic reaction coordinate (IRC) is concerned with travel along the reaction path it can be defined by the path taken by a classical particle sliding from a saddle point down to a minimum. 

Another example of slight conceptual inaccuracy is given by the Wigner function(12) and Feynman path integral(13). Both are useful ways to look at the wave function. However, because of the prominence of classical particles in these concepts, they suggest the view that QM is a variant of statistical mechanics and that it is a theory built on top of NM. This is unfortunate, since one wants to convey the notion that NM can be recovered as an integral part of QM pertaining to for macroscopic systems. 

The wave function is an irreducible entity completely defined by the Schrbdinger equation and this should be the cote of the message conveyed to students. It is not useful to introduce any hidden variables, not even Feynman paths. The wave function is an element of a well defined state space, which is neither a classical particle, nor a classical field. Its nature is fully and accurately defined by studying how it evolves and interacts and this is the only way that it can be completely and correctly understood. The evolution and interaction is accurately described by the Schrbdinger equation or the Heisenberg equation or the Feynman propagator or any other representation of the dynamical equation. 

Consider a classical particle of mass w in a parabolic potential well. At time t the displacement x of the particle from the origin is given by... 

We begin with a consideration of a classical particle i with mass mt rotating in a plane at a constant distance r, from a fixed center as shown in Figure 5.2. The time r for the particle to make a complete revolution on its circular path is equal to the distance traveled divided by its linear velocity Vi... 

This quantity is of great importance, since it actually contains all information about electron correlation, as we will see presently. Like the density, the pair density is also a non-negative quantity. It is symmetric in the coordinates and normalized to the total number of non-distinct pairs, i. e., N(N-l).8 Obviously, if electrons were identical, classical particles that do not interact at all, such as for example billiard balls of one color, the probability of finding one electron at a particular point of coordinate-spin space would be completely independent of the position and spin of the second electron. Since in our model we view electrons as idealized mass points with no volume, this would even include the possibility that both electrons are simultaneously found in the same volume element. In this case the pair density would reduce to a simple product of the individual probabilities, i.e.,... 

Let us consider the one-dimensional motion of a classical particle ( -oscillator) in a potential well of the type... 

Sometimes the theoretical or computational approach to description of molecular structure, properties, and reactivity cannot be based on deterministic equations that can be solved by analytical or computational methods. The properties of a molecule or assembly of molecules may be known or describable only in a statistical sense. Molecules and assemblies of molecules exist in distributions of configuration, composition, momentum, and energy. Sometimes, this statistical character is best captured and studied by computer experiments molecular dynamics, Brownian dynamics, Stokesian dynamics, and Monte Carlo methods. Interaction potentials based on quantum mechanics, classical particle mechanics, continuum mechanics, or empiricism are specified and the evolution of the system is then followed in time by simulation of motions resulting from these direct... 

These notations are used for positions and momenta, when the nuclei are treated as classical particles and denote average positions and momenta when they are treated quantum mechanically. 

Consider reorientations of a diatomic surface group BC (see Fig. A2.1) connected to the substrate thermostat. By a reorientation is meant a transition of the atom C from one to another well of the azimuthal potential U(qi) (see Fig. 4.4)). The terminology used implies a classical (or at least quasi-classical) description of azimuthal motion allowing the localization of the atom C in a certain well. A classical particle, with the energy lower than the reorientation barrier Awhich does not interact with the thermostat cannot leave the potential well where it was located initially. The only pathway to reorientations is provided by energy fluctuations of a particle which arise from its contact with the thermostat. Let us estimate the average frequency of reorientations in the framework of this classical approach. 

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