Density matrix coherences

Figure Al.6.18. Liouville space lattice representation in one-to-one correspondence with the diagrams in figure A1.6.17. Interactions of the density matrix with the field from the left (right) is signified by a vertical (liorizontal) step. The advantage to the Liouville lattice representation is that populations are clearly identified as diagonal lattice points, while coherences are off-diagonal points. This allows innnediate identification of the processes subject to population decay processes (adapted from [37]).

Fundamentally, the conditions for lasing are detemiined unambiguously once the populations and coherences of the system density matrix are known. Yet, we have been unable to find in the literature any simple criterion for lasing in multilevel systems in temis of the system density matrix alone. Our conjecture is that entropy, as... 

A simple, non-selective pulse starts the experiment. This rotates the equilibrium z magnetization onto the v axis. Note that neither the equilibrium state nor the effect of the pulse depend on the dynamics or the details of the spin Hamiltonian (chemical shifts and coupling constants). The equilibrium density matrix is proportional to F. After the pulse the density matrix is therefore given by and it will evolve as in equation (B2.4.27). If (B2.4.28) is substituted into (B2.4.30), the NMR signal as a fimction of time t, is given by (B2.4.32). In this equation there is a distinction between the sum of the operators weighted by the equilibrium populations, F, from the unweighted sum, 7. The detector sees each spin (but not each coherence ) equally well. 

The simplest scheme that accounts for the destruction of phase coherence is the so-called stochastic interruption model [Nikitin and Korst 1965 Simonius 1978 Silbey and Harris 1989]. Suppose the process of free tunneling is interrupted by a sequence of collisions separated by time periods vo = to do After each collision the system forgets its initial phase, i.e., the off-diagonal matrix elements of the density matrix p go to zero, resulting in the density matrix p ... 

In general the spectral one-particle density matrix p(r, rE) describes the mutual coherence of the wave field of high-energy electrons at the points r and r. For the simplest case of time-independent interaction potential the diagonal elements of... 

The analytic evaluation of the density matrix requires the diagonalization of Hi, which can be easily performed for the two extreme cases, a>r( Qg. Indeed, in the case of a low rf-field, only off-diagonal terms related to the CT are retained in the H Hamiltonian (39), which thus behaves like a fictitious spin-1/2 operator, affecting only the CT coherences /1 io- These coherences are thus selectively excited with the nutation frequency ... 

A quantum state loses quantum coherence (decoheres) when Sqd wave functions are peaked along classical trajectories. And it decoheres when each trajectory loses quantum coherence with its neighbors. Quantum decoherence is realized when the diagonal term density matrix dominates over the off-diagonal term (fts-... 

A measure for the electronic coherence of the wave function are the nondiagonal elements of the electronic density matrix, which, for example, in the diabatic representation are given by (k k )... 

Figure 15. Average number of random walkers generated for a single iteration as obtained for Model IVa [205], The full and short dashed lines correspond to the upper and lower electronic populations, respectively, while the long dashed line corresponds to the sum of the coherences of the electronic density matrix.

In Ref. [4] we have studied an intense chirped pulse excitation of a molecule coupled with a dissipative environment taking into account electronic coherence effects. We considered a two state electronic system with relaxation treated as diffusion on electronic potential energy surfaces with respect to the generalized coordinate a. We solved numerically equations for the density matrix of a molecular system under the action of chirped pulses of carrier frequency a> with temporal variation of phase [Pg.131]

We follow the method of Ref. [4] to calculate the SFG response in the time domain. The 1R polarization is calculated by solving the Schrddinger equation in the formalism of the density matrix. It is proportional to the coherence induced by the IR pulse between v=0 and v=l. The coherence is the solution of standard coupled differential equations [6]. 

A more general approach is required to interpret the current experiments, Jean and co-workers have developed multilevel Redfield theory into a versatile tool for describing ultrafast spectroscopic experiments [22-25], In this approach, terms neglected at the Bloch level play an important role for example, coherence transfer terms that transform a coherence between levels i and j into a coherence between levels j and k ( /t - = 2) or between levels k and l ( f - j - 2, k-j = 2) and couplings between populations and coherences. Coherence transfer processes can often compete effectively with vibrational relaxation and dephasing processes, as shown in Fig. 4 for a single harmonic well, initially prepared in a superposition of levels 6 and 7. The lower panel shows the population of levels 6 and 7 as a function of time, whereas the upper panels display off-diagonal density matrix ele-... 

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 growth of spherical precipitates under diffusion-limited conditions has been observed in a number of systems, such as Co-rich particles growing in Cu supersaturated with Co (see Chapter 23). In these systems, the particles are coherent with the matrix crystal and the interfaces possess high densities of coherency dislocations, which are essentially steps with small Burgers vectors, The interfaces therefore possess a high density of sites where atoms can be exchanged and the particles operate as highly efficient sources and sinks. 

The coherence transfer provides cross peaks which are antiphase for the various 7//-split components. The antiphase nature of the cross peaks then leads to partial or total cancellation of the cross peaks themselves, especially if they are phased in the absorption mode. This behavior can be simulated (Fig. 8.15) using appropriate treatments of the time evolution of the spin system, for instance using the density matrix formalism [17,18]. It is quite common that signals in paramagnetic systems... 

At T = 0 the hindered rotation is a coherent tunneling process like that studied in Section 2.3 for the double well. If, for instance, the system is initially prepared in pure state localized in one of the wells, then the density matrix in the coordinate representation is given by... 

So far, one can be much more successful in calculating a rate constant when one knows in advance that it exists, than in answering the question of whether it exists. A considerable breakthrough in this area was the solution of the spin-boson problem, which, however, has only limited relevance to any problem in chemistry because it neglects the effects of intrawell dynamics (vibrational relaxation) and does not describe thermally activated transitions. A number of attempts have been made to go beyond the two-level system approximation, but the basic question of how vibrational relaxation affects the transition from coherent oscillations to exponential decay awaits a quantitative solution. Such a solution might be obtained by numerical computation of real-time path integrals for the density matrix using the influence functional technique. 

E. Brandas, C.A. Chatzidimitriou-Dreismann, On the Connection Between Certain Properties of the Second-Order Reduced Density Matrix and the Occurrence of Coherent-Dissipative Structures in Disordered Condensed Matter, Int. J. Quant. Chem. 40 (1991) 649. 

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