Coordinates space

The calculation of the time evolution operator in multidimensional systems is a fomiidable task and some results will be discussed in this section. An alternative approach is the calculation of semi-classical dynamics as demonstrated, among others, by Heller [86, 87 and 88], Marcus [89, 90], Taylor [91, 92], Metiu [93, 94] and coworkers (see also [83] as well as the review by Miller [95] for more general aspects of semiclassical dynamics). This method basically consists of replacing the 5-fimction distribution in the true classical calculation by a Gaussian distribution in coordinate space. It allows for a simulation of the vibrational... 

Under circumstances that this condition holds an ADT matrix, A exists such that the adiabatic electronic set can be transformed to a diabatic one. Working with this diabatic set, at least in some part of the nuclear coordinate space, was the objective aimed at in [72]. 

Calculating points on a set of PES, and fitting analytic functions to them is a time-consuming process, and must be done for each new system of interest. It is also an impossible task if more than a few (typically 4) degrees of freedom are involved, simply as a consequence of the exponential growth in number of ab initio data points needed to cover the coordinate space. 

Finally, Gaussian wavepacket methods are described in which the nuclear wavepacket is described by one or more Gaussian functions. Again the equations of motion to be solved have the fomi of classical trajectories in phase space. Now, however, each trajectory has a quantum character due to its spread in coordinate space. 

For bound state systems, eigenfunctions of the nuclear Hamiltonian can be found by diagonalization of the Hamiltonian matiix in Eq. (11). These functions are the possible nuclear states of the system, that is, the vibrational states. If these states are used as a basis set, the wave function after excitation is a superposition of these vibrational states, with expansion coefficients given by the Frank-Condon overlaps. In this picture, the dynamics in Figure 4 can be described by the time evolution of these expansion coefficients, a simple phase factor. The periodic motion in coordinate space is thus related to a discrete spectrum in energy space. 

Importantly, this term is a derivative (nonlocal) operator on the nuclear coordinate space. 

The diabatic electronic functions are related to the adiabatic functions by unitary transformations at each point in coordinate space... 

From the preceding analysis, it is seen that the coordinate space neai R can be usefully partitioned into the branching space described in tenns of intersection adapted coordinates (p, 9, ) or (x,y,z) and its orthogonal complement the seam space spanned by a set of mutually orthonormal set w, = 4 — M . From Eq. (27), spherical radius p is the parameter that lifts the degeneracy linearly in the branching space spanned by x, y, and z. 

It has to be emphasized that in this framework J is the angular momentum operatoi in ordinary coordinate space (i.e., configuration space) and 0 is a (differential) ordinary angular polar coordinate. 

These difficulties have led to a revival of work on internal coordinate approaches, and to date several such techniques have been reported based on methods of rigid-body dynamics [8,19,34-37] and the Lagrange-Hamilton formalism [38-42]. These methods often have little in common in their analytical formulations, but they all may be reasonably referred to as internal coordinate molecular dynamics (ICMD) to underline their main distinction from conventional MD They all consider molecular motion in the space of generalized internal coordinates rather than in the usual Cartesian coordinate space. Their main goal is to compute long-duration macromolecular trajectories with acceptable accuracy but at a lower cost than Cartesian coordinate MD with bond length constraints. This task mrned out to be more complicated than it seemed initially. 

II. NORMAL MODE ANALYSIS IN CARTESIAN COORDINATE SPACE... 

As discussed before, the mass renormalization is a reflection of the fact that the particle traces a distance longer than 2Qq in the total multidimensional coordinate space. 

The state of any particle at any instant is given by its position vector q and its linear momentum vector p, and we say that the state of a particle can be described by giving its location in phase space. For a system of N atoms, this space has 6iV dimensions three components of p and the three components of q for each atom. If we use the symbol F to denote a particular point in this six-dimensional phase space (just as we would use the vector r to denote a point in three-dimensional coordinate space) then the value of a particular property A (such as the mutual potential energy, the pressure and so on) will be a function of r and is often written as A(F). As the system evolves in time then F will change and so will A(F). 

New Insights into the data. Mapping our data into an appropriate factor space can provide a new frame of reference wherein patterns that were not apparent in the native coordinate space become evident. Factor spaces can help us understand how many components are actually present, or which samples are similar or different to which other samples. 

Creation and Annihilation Operators.—In the last section there was a hint that the theory could handle problems in which populations do not remain constant. Thus < , < f>s 2 is the probability density in 3A -coordinate space that the occupation numbers are , and the general symmetrical state, Eq. (8-101), is one in which there is a distribution of probabilities over different sets of occupation numbers the sum over sets could easily be extended to include sets corresponding to different total populations N. 

Consider next the projection operator upon the coordinate space eigenvector X) ... 

It is worthwhile to consider the same theorem in terms of coordinate space instead of occupation number space. Thus, we may envision an ensemble of systems whose states are X>, and whose distribution probabilities among these states are w(X). We define the density operator... 

At the end of Section 8.16 we mentioned that the Fock representation avoids the use of multiple integrations of coordinate space when dealing with the many-body problem. We can see here, however, that the new method runs into complications of its own To handle the immense bookkeeping problems involved in the multiple -integrals and the ordered products of creation and annihilation operators, special diagram techniques have been developed. These are discussed in Chapter 11, Quantum Electrodynamics. The reader who wishes to study further the many applications of these techniques to problems of quantum statistics will find an ample list of references in a review article by D. ter Haar, Reports on Progress in Physics, 24,1961, Inst, of Phys. and Phys. Soc. (London). 

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