Quantum-classical Liouville equation results

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 evolution equations for the quantities entering the right side of this equation are obtained by substitution into the quantum-classical Liouville equation. For a variety of one- and two-dimensional systems for which exact results are known, excellent agreement was found. 

We have thus reconstructed the derivation and interpreted the results of Ref [15], The first two terms, i.e., the commutator and the Poisson brackets, are already present in a theory based on the quantum-classical Liouville representation discussed in section 1. The new term, which appears within the Heisenberg group approach, needs to be explained. In the attempt to provide a physical interpretation to this term we have shown, in Ref. [1], that the new equation of motion is purely classical. This will be illustrated in the following section. 

PESs, and (iv) obey the principle of microreversibility. Section 3 describes in some detail the mean-field trajectory method and also discusses its connection to time-dependent self-consistent-field schemes. The surface-hopping method is considered in Sec. 4, which discusses various motivations of the ansatz as well as several variants of the implementation. Section 5 gives a brief account on the quantum-classical Liouville description and considers the possibility of an exact stochastic realization of its equation of motion. The mapping formalism, its relation to other formulations, and its quasi-classical implementation is introduced in Sec. 6. Section 7 is concerned with the semiclassical description of nonadiabatic quantum mechanics. Section 8 summarizes our results and concludes with some general remarks. 

The crisis of the GME method is closely related to the crisis in the density matrix approach to wave-function collapse. We shall see that in the Poisson case the processes making the statistical density matrix become diagonal in the basis set of the measured variable and can be safely interpreted as generators of wave function collapse, thereby justifying the widely accepted conviction that quantum mechanics does not need either correction or generalization. In the non-Poisson case, this equivalence is lost, and, while the CTRW perspective yields correct results, no theoretical tool, based on density, exists yet to make the time evolution of a contracted Liouville equation, classical or quantum, reproduce them. 

A second problem with the GME derived from the contraction over a Liouville equation, either classical or quantum, has to do with the correct evaluation of the memory kernel. Within the density perspective this memory kernel can be expressed in terms of correlation functions. If the linear response assumption is made, the two-time correlation function affords an exhaustive representation of the statistical process under study. In Section III.B we shall see with a simple quantum mechanical example, based on the Anderson localization, that the second-order approximation might lead to results conflicting with quantum mechanical coherence. 

If the thermal equilibration of states 2 and 3 is very slow, the osciUatimis between states 1 and 2 continue indefinitely (Fig. 10.4A). As the time cmistant for conversion of state 2 to state 3 is decreased, the oscillations are damped and state 3 is formed more rapidly (Fig. 10.4B-D). But when Ti becomes much less than hlH2i, the rate of formation of state 3 decreases again (Fig. 10.4E,F) This quantum mechanical effect is completely contrary to what one would expect from a classical kinetic model of a two-step process, where increasing the rate constant for conversion of the intermediate state to the final product can only speed up the overall reaction (Box 10.2). In the stochastic Liouville equation, the slowing of the overall process results from very rapid quenching of the off-diagonal terms of p by the stochastic decay of state 2. This is essentially the same as the slowing of equilibration of two quantum states when is much less than h/Hi2, which we saw in Fig. 10.3. 

---