Time-evolution matrix

The reduction schemes used by Tang et al. [20] to define the surrogate fewer state system follows the method proposed by Shore [62]. The scheme has a compact form when we introduce two orthogonal projection operators P and Q and work in the frequency domain instead of the time domain. The time evolution matrix for the n-state system dynamics, U(f). and its Fourier transform, G(w), satisfy the following equations ... 

For themial unimolecular reactions with bimolecular collisional activation steps and for bimolecular reactions, more specifically one takes the limit of tire time evolution operator for - co and t —> + co to describe isolated binary collision events. The corresponding matrix representation of f)is called the scattering matrix or S-matrix with matrix elements... 

A diagrannnatic approach that can unify the theory underlymg these many spectroscopies is presented. The most complete theoretical treatment is achieved by applying statistical quantum mechanics in the fonn of the time evolution of the light/matter density operator. (It is recoimnended that anyone interested in advanced study of this topic should familiarize themselves with density operator fonnalism [8, 9, 10, H and f2]. Most books on nonlinear optics [13,14, f5,16 and 17] and nonlinear optical spectroscopy [18,19] treat this in much detail.) Once the density operator is known at any time and position within a material, its matrix in the eigenstate basis set of the constituents (usually molecules) can be detennined. The ensemble averaged electrical polarization, P, is then obtained—tlie centrepiece of all spectroscopies based on the electric component of the EM field. 

The main cost of this enlianced time resolution compared to fluorescence upconversion, however, is the aforementioned problem of time ordering of the photons that arrive from the pump and probe pulses. Wlien the probe pulse either precedes or trails the arrival of the pump pulse by a time interval that is significantly longer than the pulse duration, the action of the probe and pump pulses on the populations resident in the various resonant states is nnambiguous. When the pump and probe pulses temporally overlap in tlie sample, however, all possible time orderings of field-molecule interactions contribute to the response and complicate the interpretation. Double-sided Feymuan diagrams, which provide a pictorial view of the density matrix s time evolution under the action of the laser pulses, can be used to detenuine the various contributions to the sample response [125]. 

In matrix block form the equations that govern the time evolution of the parameters can be expressed as... 

The problem is then reduced to the representation of the time-evolution operator [104,105]. For example, the Lanczos algorithm could be used to generate the eigenvalues of H, which can be used to set up the representation of the exponentiated operator. Again, the methods are based on matrix-vector operations, but now much larger steps are possible. 

As shown above in Section UFA, the use of wavepacket dynamics to study non-adiabatic systems is a trivial extension of the methods described for adiabatic systems in Section H E. The equations of motion have the same form, but now there is a wavepacket for each electronic state. The motions of these packets are then coupled by the non-adiabatic terms in the Hamiltonian operator matrix elements. In contrast, the methods in Section II that use trajectories in phase space to represent the time evolution of the nuclear wave function cannot be... 

Associated with the pole of the S-matrix is a Seigert state, I-Ves, which has purely outgoing boundary conditions and satisfies (with some caveats) the equation, // I res = z les,H being the system Hamiltonian.44 If a square integrable approximation to I res is constructed, then its time evolution, k . (/,), wiH exhibit pure exponential decay after a transient induction period. Of course any L2 state will show quadratic, and hence non-exponential, decay at short times since... 

Figure 5. Schematic illustration of the time evolution of a time-displaced basis. Basis states 1, 2, and 3 belong to one seed while 4, 5, and 6 belong to another. The basis set is shown at two time points, and the leading basis functions are shaded in gray. The arrows connecting basis functions indicate required new matrix elements at time t + At. For this specific example, 11 new matrix elements are evaluated at each point in time, compared to 21 if all basis functions had been chosen independently. (Figure adapted from Ref. 40.)...

The results of this test of the TDB-FMS method are encouraging, and we expect the gain in efficiency to be more significant for larger molecules and/or longer time evolutions. Furthermore, as noted briefly before, the approximate evaluation of matrix elements of the Hamiltonian may be improved if we can further exploit the temporal nonlocality of the Schrodinger equation. 

For bound state systems, eigenfunctions of the nuclear Hamiltonian can be found by diagonalization of the Hamiltonian matrix 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 spectmm in energy space. 

By construction Eq. (38) associated with observables, describes the mass-shell condition, while Eq. (43) is a density matrix equation giving the time-evolution of the state l/. That this is so can be seen in the following way. Considering Eqs. (41), let us multiply Eq. (43) by ), that is... 

The distinctive feature of the dynamic case is the time evolution of the estimate and its error covariance matrix. Their time dependence is given by... 

These new trajectories are the so-called reduced quantum trajectories [30], which are only explicitly related to the system reduced density matrix. The dynamics described by Equation 8.42 leads to the correct intensity (time evolution of which is described by Equation 8.40) when the statistics of a large number of particles are considered. Moreover, Equation 8.42 reduces to the well-known expression for the velocity held in Bohmian mechanics, when there is no interaction with the environment. 

The notion of chaos is interwoven with the discussion of time evolution, which we do not pursue in this volume. It is worthwhile, however, to note that it is, by now, well understood that a quantum-mechanical system with a finite Hamiltonian matrix cannot satisfy many of the purely mathematical characterizations of chaos. Equally, however, over long periods of time such systems can manifest many of the qualitative features that one associates with classically chaotic systems. It is not our intention to follow this most interesting theme. Instead we seek a more modest aim, namely, to forge a link between the elementary notions of classical nonlinear dynamics and the algebraic approach. This turns out to be possible using the action-angle variables of classical mechanics. In this section we consider only the nonlinear dynamics aspects. We complete the bridge in Chapter 7. 

In this book we shall write the Hamiltonian as an (algebraic) operator using the appropriate Lie algebra. We intend to illustrate by many applications what we mean by this cryptic statement. It is important to emphasize that one way to represent such a Hamiltonian is as a matrix. In this connection we draw attention to one important area of spectroscopy, that of electronically excited states of larger molecules,4 which is traditionally discussed in terms of matrix Hamiltonians, the simplest of which is the so-called picket fence model (Bixon and Jortner, 1968). A central issue in this area of spectroscopy is the time evolution of an initially prepared nonstationary state. We defer a detailed discussion of such topics to a subsequent volume, which deals with the algebraic approach to dynamics. 

Poliak and Eckhardt have shown that the QTST expression for the rate (Eq. 52) may be analyzed within a semiclassical context. The result is though not very good at very low temperatures, it does not reduce to the low temperature ImF result. The most recent and best resultthus far is the recent theory of Ankerhold and Grabert," who study in detail the semiclassical limit of the time evolution of the density matrix and extract from it the semiclassical rate. Application to the symmetric one dimensional Eckart barrier gives very good results. It remains to be seen how their theory works for asymmetric and dissipative systems. 

Consider now the equality Hoj> n Jm=8j>j. Thus, in this model, preparing the system in the ground state of the Coulomb Hamiltonian, no time evolution can be expected if we do not switch on the kinematic couplings. We take a simple case where the electron-phonon coupling is on. The matrix elements of H in this base set look like ... 

The time evolution operator propagates an arbitrary quantum state thanks to the non-zero matrix elements (Ve0ph)j m ,jm- The set ( )j(q)Qm(Q) has all electronic base states corresponding to all possible chemical species in the sense discussed above only because the generalized electronic diabatic set is complete. 

Figure 6. Coherent population dynamics calculated using the density matrix equation (3) for different delays (a-c) of the laser pulses. Upper part Time evolution of the Rabi frequencies of both laser pulses. Lower part Calculated time evolution of the level populations for three different delays.

The time evolution is determined by the full effective Hamiltonian H and not by the rate matrix T alone. One cannot therefore discuss the time evolution without reference to the matrix H. Say, however, H and T commute, [H, T] = 0. A simple condition that ensures this result is that the bound states are strictly degenerate. If H and T commute, the eigenvectors of T evolve in time independently of one another. In the basis of states defined by the N eigenvectors of T there will be K states that will decay by direct coupling to the continuum and N - K states that are trapped forever. An arbitrary initial state is a linear combination of the N eigenvectors of T and hence can have a trapped component. 

The final state of the system, corresponding to the ground state of the molecule plus a photon, is represented by ipB = 0 k, e>. and the set 0, are the eigenfunctions of Hth while vac ) and k, e) represent the zero-photon and the one-photon eigenstates of HR, respectively. The time evolution of the amplitudes a,(t) and CE(t) can be computed from time-dependent perturbation theory. The equations of motion are determined by the energy levels of the zero-order states of Hel + HR, by the coupling matrix elements... 

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