Density matrix treatment motions

INTRODUCTION DENSITY MATRIX TREATMENT Equation of motion for the density operator Variational method for the density amplitudes THE EIKONAL REPRESENTATION The eikonal representation for nuclear motions... 

The treatment presented so far is quite general and formally exact. It combines the eikonal representation for nuclear motions and the time-dependent density matrix in an approach which could be named as the Eik/TDDM approach. The following section reviews how the formalism can be implemented in the eikonal approximation of short wavelengths for the nuclear motions, and for specific choices of electronic states leading to the TDHF equations for the one-electron density matrix, and to extensions of TDHF. 

A formulation of electronic rearrangement in quantum molecular dynamics has been based on the Liouville-von Neumann equation for the density matrix. Introducing an eikonal representation, it naturally leads to a general treatment where Hamiltonian equations for nuclear motions are coupled to the electronic density matrix equations, in a formally exact theory. Expectation values of molecular operators can be obtained from integrations over initial conditions. 

The Eik/TDDM approximation can be computationally implemented with a procedure based on a local interaction picture for the density matrix, and on its propagation in a relax-and-drive perturbation treatment with a relaxing density matrix as the zeroth-order contribution and a correction due to the driving effect of nuclear motions. This allows for an efficient computational procedure for differential equations coupling functions with short and long time scales, and is of general applicability. 

The theory described so far is based on the Master Equation, which is a sort of intermediate level between the macroscopic, phenomenological equations and the microscopic equations of motion of all particles in the system. In particular, the transition from reversible equations to an irreversible description has been taken for granted. Attempts have been made to derive the properties of fluctuations in nonlinear systems directly from the microscopic equations, either from the classical Liouville equation 18 or the quantum-mechanical equation for the density matrix.19 We shall discuss the quantum-mechanical treatment, because the formalism used in that case is more familiar. 

For a pulse-type NMR experiment, the assumption has a straightforward interpretation, since the pulse applied at the moment zero breaks down the dynamic history of the spin system involved. The reasoning presented here, which leads to the equation of motion in the form of equation (72), bears some resemblance to Kaplan and Fraenkel s approach to the quantum-mechanical description of continuous-wave NMR. (39) The crucial point in our treatment is the introduction of the probabilities izUa which are expressed in terms of pseudo-first-order rate constants. This makes possible a definition of the mean density matrix pf of a molecule at the moment of its creation, even for complicated multi-reaction systems. The definition of the pf matrix makes unnecessary the distinction between intra- and inter-molecular spin exchange which has so far been employed in the literature. 

In this review, we begin with a treatment of the functional theory employing as basis the maximum entropy principle for the determination of the density matrix of equilibrium ensembles of any system. This naturally leads to the time-dependent functional theory which will be based on the TD-density matrix which obeys the von Neumann equation of motion. In this way, we present a unified formulation of the functional theory of a condensed matter system for both equilibrium and non-equilibrium situations, which we hope will give the reader a complete picture of the functional approach to many-body interacting systems of interest to condensed matter physics and chemistry. 

In the remainder of this chapter, we now focus on one specific mefhod nof discussed so far, fhe Liouville-von Neumann approach in TDDFT. This scheme falls under point 2.2.2 from above as the contacts are treated as semi-infinite leads. In contrast to the approach by Kurth et al. [41], the basic variable is the Kohn-Sham one-particle density matrix rather than the Kohn-Sham orbitals. We begin with a discussion on the formal foundations of the method, before the relevant equations of motion are presented. Special emphasis is also laid on the exact treatment of the contacts in the hierarchical equation of motion approach. 

From a quantum mechanical perspective, the treatment of the laser-adsorbate interaction can be straightforwardly included in the equations of motion for the reduced density matrix. Since the molecules are only of modest size compared to the wavelength of the incoming electric field, F t), the interaction can be treated within the semi-classical dipole approximation, i.e. the system Hamiltonian is replaced by... 

Note that, since the coherences of the reduced density matrix vanish on long timescales, the coupling to the STM electric field disappears from the equations of motion and only the incoherently driven evolution of the system mediated by the non-adiabatic couplings remains. This is consistent with the picture of an ensemble of localized states in quasi-thermal equilibrium that diffuses towards other local minima. Since the zeroth-order vibrational states are non-local by constmction, both tunneling and above-threshold excitations are seamlessly included in this treatment. 

In the first part to follow, the equations of motion of a soft solid are written in the harmonic approximation. The matrices that describe the potential, and hence the structure, of the material are then considered in a general way, and their properties under a normal mode transformation are discussed. The same treatment is given to the dissipation terms. The long wavelength end of the spectral density is of interest, and here it seems that detailed matrix calculations can be replaced by simple scaling arguments. This shows how the inertial term, usually absent in molecular problems, is magnified to become important in the continuum limit. 

This text of the two-volume treatment contains most of the theoretical background necessary to understand experiments in the field of phonons. This background is presented in four basic chapters. Chapter 2 starts with the diatomic linear chain. In the classical theory we discuss the periodic boundary conditions, equation of motion, dynamical matrix, eigenvalues and eigenvectors, acoustic and optic branches and normal coordinates. The transition to quantum mechanics is achieved by introducing the Sohpddingev equation of the vibrating chain. This is followed by the occupation number representation and a detailed discussion of the concept of phonons. The chapter ends with a discussion of the specific heat and the density of states. 

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