Classical Liouville equation

A particularly convenient notation for trajectory bundle system can be introduced by using the classical Liouville equation which describes an ensemble of Hamiltonian trajectories by a phase space density / = f q, q, t). In textbooks of classical mechanics, e.g. [12], it is shown that Liouville s equation... 

A partial differential equation is then developed for the number density of particles in the phase space (analogous to the classical Liouville equation that expresses the conservation of probability in the phase space of a mechanical system) (32>. In other words, if the particle states (i.e. points in the particle phase space) are regarded at any moment as a continuum filling a suitable portion of the phase space, flowing with a velocity field specified by the function u , then one may ask for the density of this fluid streaming through the phase space, i.e. the number density function n(z,t) of particles in the phase space defined as the number of particles in the system at time t with phase coordinates in the range z (dz/2). 

The similar appearance of the quantum and classical Liouville equations has motivated several workers to construct a mixed quantum-classical Liouville (QCL) description [27 4]. Hereby a partial classical limit is performed for the heavy-particle dynamics, while a quantum-mechanical formulation is retained for the light particles. The quantities p(f) and H in the mixed QC formulation are then operators with respect to the electronic degrees of freedom, described by some basis states 4> ), and classical functions with respect to the nuclear degrees of freedom with coordinates x = x, and momenta p = pj — for example. 

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... 

When the quantum-classical Liouville equation is expressed in the adiabatic basis, the most difficult terms to simulate come from the off-diagonal force matrix elements, which give rise to the nonadiabatic coupling matrix elements. As described above, contributions coming from this term were computed using the momentum-jump approximation in the context of a surface-hopping scheme. 

One way to simplify this term in the evolution equation is to make use of a basis that diagonalizes the force contribution [42] i.e., we represent the quantum-classical Liouville equation in a basis i R) such that... 

The quantum-classical Liouville equation in the force basis has been solved for low-dimensional systems using the multithreads algorithm [42,43]. Assuming that the density matrix is localized within a small volume of the classical phase space, it is written as linear combination of matrices located at L discrete phase space points as... 

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. 

The quantum-classical Liouville equation was expressed in the subsystem basis in Sec. 3.1. Based on this representation, it is possible to recast the equations of motion in a form where the discrete quantum degrees of freedom are described by continuous position and momentum variables [44-49]. In the mapping basis the eigenfunctions of the n-state subsystem can be replaced with eigenfunctions of n fictitious harmonic oscillators with occupation numbers limited to 0 or 1 A) —> toa) = 0i, , 1a, -0 ). This mapping basis representation then makes use of the fact that the matrix element of an operator Bw(X) in the subsystem basis, B y (X), can be written in mapping form as B(( (X) = (AIBy X A ) = m Bm(X) mx>), where... 

Given this correspondence between the matrix elements of a partially Wigner transformed operator in the subsystem and mapping bases, we can express the quantum-classical Liouville equation in the continuous mapping coordinates [53]. The first step in this calculation is to introduce an n-dimensional coordinate space representation of the mapping basis,... 

Carrying out the this change of representation on the quantum-classical Liouville equation and using the product rule formula for the Wigner transform... 

We now show how the mean field equations can be derived as an approximation to the quantum-classical Liouville equation (8) [9]. The Hamiltonian... 

If we substitute the above expression for pw X,t) into the quantum-classical Liouville equation we find... 

To take the quantum-classical limit of this general expression for the transport coefficient we partition the system into a subsystem and bath and use the notation 1Z = (r, R), V = (p, P) and X = (r, R,p, P) where the lower case symbols refer to the subsystem and the upper case symbols refer to the bath. To make connection with surface-hopping representations of the quantum-classical Liouville equation [4], we first observe that AW(X 1) can be written as... 

We have presented some of the most recent developments in the computation and modeling of quantum phenomena in condensed phased systems in terms of the quantum-classical Liouville equation. In this approach we consider situations where the dynamics of the environment can be treated as if it were almost classical. This description introduces certain non-classical features into the dynamics, such as classical evolution on the mean of two adiabatic surfaces. Decoherence is naturally incorporated into the description of the dynamics. Although the theory involves several levels of approximation, QCL dynamics performs extremely well when compared to exact quantum calculations for some important benchmark tests such as the spin-boson system. Consequently, QCL dynamics is an accurate theory to explore the dynamics of many quantum condensed phase systems. 

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. 

I. Horenko, B. Schmidt, and C. Schutte. A theoretical model for molecules interacting with intense laser pulses The floquet-based quantum-classical Liouville equation. The Journal of Chemical Physics, 115(13) 5733-5743, 2001. 

The quantum-classical Liouville equation is obtained from this equation by introducing scaled variables such that the characteristic momenta of the light and heavy degrees of freedom are comparable. This scaling introduces a small parameter p = (m/M)1/2 in the equations of motion. Expansion of the quantum Liouville operator to 0 p) yields the quantum-classical Liouville equation [2,4,12-20],... 

J. Ma, D. Hsu, J.E. Straub, Approximate solution of the classical Liouville equation using Gaussian phase packet dynamics application to enhanced equilibrium averaging and global optimization, J. Chem. Phys. 99 (1993), 4024. 

M.J. Field, Global optimization using ab initio quantum mechanical potentials and simulated annealing of the classical Liouville equation, J. Chem. Phys. 103 (1995), 3621. 

The classical limit of these equations of motion is easily taken by retaining only the term independent of h in the Liouville operator iLw = jHw X)sm ( ) = Hw X)A + 0 h). Using this result we find the classical Liouville equation for the density matrix. 

To obtain the second approximate equality we expanded the right hand side to first order in the small parameter p = mlM) ". Returning to unsealed units we have the quantum-classical Liouville equation,... 

The quantum-classical Liouville equation may be expressed in any convenient basis. In particular, the adiabatic basis vectors, a R), are given by... 

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