Time-independent

Now consider die case where Ais itself a time-independent operator, such as that for the position, momenPiin or angidar momenPiin of a particle or even the energy of the benzene molecule. In these cases, the time-dependent expansion coefficients are unaffected by application of the operator, and one obtains... 

Since in this case the Flamiltonian is time independent, the general solution can be written as... 

This expression assumes a system with a discrete level structure for systems with both a discrete and a continuous portion to their spectrum the expression consists of a sum over the discrete states and an integral over the continuous states.) Flere, ifi (v) is a solution of the time-independent Sclirodinger equation,... 

The populations, /Q, appear on the diagonal as expected, but note that there are no off-diagonal elements—no coherences this is reasonable since we expect the equilibrium state to be time-independent, and we have associated the coherences with time. 

Defining EJh + oij, replacing v /(-co) by v r(0), since the difference is only a phase factor, which exactly cancels in the bra and ket, and assuming that the electric field vector is time independent, we find... 

The microcanonical ensemble is a certain model for the repetition of experiments in every repetition, the system has exactly the same energy, Wand F but otherwise there is no experimental control over its microstate. Because the microcanonical ensemble distribution depends only on the total energy, which is a constant of motion, it is time independent and mean values calculated with it are also time independent. This is as it should be for an equilibrium system. Besides the ensemble average value (il), another coimnonly used average is the most probable value, which is the value of tS(p, q) that is possessed by the largest number of systems in the ensemble. The ensemble average and the most probable value are nearly equal if the mean square fluctuation is small, i.e. if... 

The equilibrium state for a gas of monoatomic particles is described by a spatially unifonn, time independent distribution fiinction whose velocity dependence has the fomi of the Maxwell-Boltzmaim distribution, obtained from equilibrium statistical mechanics. That is,/(r,v,t) has the fomi/" (v) given by... 

It is clear from figure A3.4.3 that the second-order law is well followed. Flowever, in particular for recombination reactions at low pressures, a transition to a third-order rate law (second order in the recombining species and first order in some collision partner) must be considered. If the non-reactive collision partner M is present in excess and its concentration [M] is time-independent, the rate law still is pseudo-second order with an effective second-order rate coefficient proportional to [Mj. 

With time independent matrix K it has the general solution... 

This section is divided into two sections the first concerned with time-dependent methods for describing the evolution of wavepackets and the second concerned with time-independent methods for solving the time independent Sclirodinger equation. The methods described are designed to be representative of what is in use. 

The eventual goal in soattering oaloulations is essentially to obtain the soattering matrix, S (see Seetion A3.11 and equation (B3.4.4) below). The soattering matrix ean be obtained by referenee to the solution of the time-independent Solirodinger equation, fiilfilling... 

The approaches discussed so far are generally called time-independent methods, since they start from the time-independent Scln-ddinger equation, (//-E)l f(t. An alternative is to use the time-dependent Scln-ddinger equation [28, 29, 59, and M. Conceptually, tlie time-dependent approach is... 

Neuhauser D and Baer M 1990 A new accurate (time independent) method for treating three-dimensional reactive collisions the application of optical potentials and projection operators J. Chem. Phys. 92 3419... 

Peskin U, Miller W H and Ediund A 1995 Quantum time evolution in time-dependent fields and time-independent reactive-scattering calculations via an efficient Fourier grid preconditioner J. Chem. Phys. 103 10 030... 

Kroes G J and Neuhauser D 1996 Performance of a time-independent scattering wave packet technique using real operators and wave functions J. Chem. Phys. 105 8690... 

Kouri D J, Huang Y, Zhu W and Hoffman D K 1994 Variational principles for the time-independent wave-packet-Schrddinger and wave-packet-Lippmann-Schwinger equations J. Chem. Phys. 100... 

Baer M, Yahalom A and Engelman R 1998 Time-dependent and time-independent approaches to study effects of degenerate electronic states J. Chem. Phys. 109 6550... 

Attractors can be simple time-independent states (points in F), limit cycles (simple closed loops in F) corresponding to oscillatory variations of tire chemical concentrations with a single amplitude, or chaotic states (complicated trajectories in F) corresponding to aperiodic variations of tire chemical concentrations. To illustrate... 

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