Liouville formalism

Since we have discovered the underlying Hamiltonian structure of the QCMD model we are able to apply methods commonly used to construct suitable numerical integrators for Hamiltonian systems. Therefore we transform the QCMD equations (1) into the Liouville formalism. To this end, we introduce a new state z in the phase space, z = and define the nonlinear... 

In the papers by Berk et al. (42) the EPR linewidths of triplet excitons in single-crystal pyrene at room temperature have been measured in experiments performed at 24 GHz. The data are fitted to a formula first presented by Reineker (43) in a theory based on the Haken-Strobl-Reineker model of exciton motion (the Haken-Strobl-Reineker model can be applied for triplet excitons because they have an exciton bandwidth small in comparison with the thermal energy ksT for more details see the review paper by Reineker (44)). This formula was rederived in the paper by Berk et al. (42) more directly from Blume s stochastic Liouville formalism (45). The agreement was excellent. This result again implied that the dominant spin-relaxation mechanism in pyrene, as in anthracene and presumably in similar molecular crystals, results from hopping between differently oriented molecules in the unit cell. 

The idea is now to replace the formal solution of the Liouville equation by the discretized version. The middle term gf the propagator in Eq. (51) can be further decomposed by an additional Trotter factorization to obtain... 

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. 

Our analysis is based on solution of the quantum Liouville equation in occupation space. We use a combination of time-dependent and time-independent analytical approaches to gain qualitative insight into the effect of a dissipative environment on the information content of 8(E), complemented by numerical solution to go beyond the range of validity of the analytical theory. Most of the results of Section VC1 are based on a perturbative analytical approach formulated in the energy domain. Section VC2 utilizes a combination of analytical perturbative and numerical nonperturbative time-domain methods, based on propagation of the system density matrix. Details of our formalism are provided in Refs. 47 and 48 and are not reproduced here. 

Section II deals with the general formalism of Prigogine and his co-workers. Starting from the Liouville equation, we derive an exact transport equation for the one-particle distribution function of an arbitrary fluid subject to a weak external field. This equation is valid in the so-called "thermodynamic limit , i.e. when the number of particles N —> oo, the volume of the system 2-> oo, with Nj 2 = C finite. As a by-product, we obtain very easily a formulation for the equilibrium pair distribution function of the fluid as well as a general expression for the conductivity tensor. 

The formal similarity between Eq. (10) and the time-dependent Schrodinger equation is striking, and we shall indeed develop methods which are very reminiscent of quantum mechanics. In particular, we may calculate the eigenfunctions and eigenvalues of the unperturbed Liouville operator L0. We look for solutions of ... 

One such systematic generalization was obtained by Cohen,8 whose method is now given the point of departure was the expansion in clusters of the non-equilibrium distribution functions. This procedure is formally analogous to the series expansion in the activity where the integrals of the Ursell cluster functions at equilibrium appear in the coefficients. Cohen then obtained two expressions in which the distribution functions of one and two particles are given in terms of the solution of the Liouville equation for one particle. The elimination of this quantity between these two expressions is a problem which presents a very full formal analogy with the elimination (at equilibrium) of the activity between the Mayer equation for the concentration and the series... 

On the other hand, the solution of the Liouville equation (2) is written formally ... 

The research was greatly facilitated by two important elements. The (formal, perturbative) solution of the Liouville equation is greatly simplified by a Fourier representation (see Appendix). The latter allows one to easily identify the various types of statistical correlations between the particles. The traditional dynamics thus becomes a dynamics of correlations. The latter is completed by... 

The basic idea of the slow-motion theory is to treat the electron spin as a part of the lattice and limit the spin part of the problem to the nuclear spin rather than the IS system. The difficult part of the problem is to treat, in an appropriate way, the combined lattice, now containing the classical degrees of freedom (such as rotation in condensed matter) as well as quantized degrees of freedom (such as the electron Zeeman interaction). The Liouville superoperator formalism is very well suited for treating this type of problems. 

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. 

Abstract. In this chapter we discuss approaches to solving quantum dynamics in the condensed phase based on the quantum-classical Liouville method. Several representations of the quantum-classical Liouville equation (QCLE) of motion have been investigated and subsequently simulated. We discuss the benefits and limitations of these approaches. By making further approximations to the QCLE, we show that standard approaches to this problem, i.e., mean-field and surface-hopping methods, can be derived. The computation of transport coefficients, such as chemical rate constants, represent an important class of problems where the QCL method is applicable. We present a general quantum-classical expression for a time-dependent transport coefficient which incorporates the full system s initial quantum equilibrium structure. As an example of the formalism, the computation of a reaction rate coefficient for a simple reactive model is presented. These results are compared to illuminate the similarities and differences between various approaches discussed in this chapter. 

The quantum-classical Liouville equation can be derived by formally expanding the operator on the right side of Eq. (6) to O(h0). One may justify [4] such an expansion for systems where the masses of particles in the environment are much greater than those of the subsystem, M > tn. In this case the small parameter in the theory is p = (m/Mj1/2. This factor emerges in the equation of motion quite naturally through a scaling of the variables motivated... 

Q. Shi and E. Geva. A derivation of the mixed quantum-classical Liouville equation from the influence functional formalism. J. Chem. Phys., 121(8) 3393-3404, 2004. 

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