Spectral density spectrum

The formal structure of (5.77) suggests that the reaction coordinate Q can be combined with the bath coordinates to form a new fictitious bath , so that the Hamiltonian takes the standard form of dissipative TLS (5.55). Suppose that the original spectrum of the bath is ohmic, with friction coefficient q. Then diagonalization of the total system (Q, qj ) gives the new effective spectral density [Garg et al. 1985]... 

The energy spectral density function (or power spectrum) P f) is given by the absolute square of P f) ... 

Let us consider the quasi-classical formulation of impact theory. A rotational spectrum of ifth order at every value of co is a sum of spectral densities at a given frequency of all J-components of all branches... 

As pointed out in the previous section, the Chebyshev operator can be viewed as a cosine propagator. By analogy, both the energy wave function and the spectrum can also be obtained using a spectral method. More specifically, the spectral density operator can be defined in terms of the conjugate Chebyshev order (k) and Chebyshev angle (0) 128 132... 

Fig. 6 Trace (a) is the power spectral density of the original spectrum o(x), trace (e) the power spectral density of the convolved spectrum /(jc). Traces (b), (c), and (d) are the power spectra of the following smoothing filters 5-point quadratic, 13-point quartic, and multismooth (a convolution of a 5-point quadratic, a 7-point quadratic, an 11-point quartic, and a 13-point quartic.

All that remains to be done for determining the fluctuation spectrum is to compute the conditional average, Eq. (31). However, this involves the full equations of motion of the many-body system and one can at best hope for a suitable approximate method. There are two such methods available. The first method is the Master Equation approach described above. Relying on the fact that the operator Q represents a macroscopic observable quantity, one assumes that on a coarse-grained level it constitutes a Markov process. The microscopic equations are then only required for computing the transition probabilities per unit time, W(q q ), for example by means of Dirac s time-dependent perturbation theory. Subsequently, one has to solve the Master Equation, as described in Section TV, to find both the spectral density of equilibrium fluctuations and the macroscopic phenomenological equation. 

We will first consider the error bounds for a spectral density broadened by a Lorentzian slit function, Eq. (15), describing the response to an exponentially damped perturbation. In this case the broadened spectrum,... 

Similar methods have been used to integrate thermodynamic properties of harmonic lattice vibrations over the spectral density of lattice vibration frequencies.21,34 Very accurate error bounds are obtained for properties like the heat capacity,34 using just the moments of the lattice vibrational frequency spectrum.35 These moments are known35 in terms of the force constants and masses and lattice type, so that one need not actually solve the lattice equations of motion to obtain thermodynamic properties of the lattice. In this way, one can avoid the usual stochastic method36 in lattice dynamics, which solves a random sample of the (factored) secular determinants for the lattice vibration frequencies. Figure 3 gives a typical set of error bounds to the heat capacity of a lattice, derived from moments of the spectrum of lattice vibrations.34 Useful error bounds are obtained... 

If we again consider Fig. 21.4, we can see that the cross section vanishes at v2 = 0.32 and that the profile does not match the spectral density, A2, of the autoionizing state. The Beutler-Fano profile of Fig. 21.4 is periodic in v2 with period 1, so the spectrum from the ground state consists of a series of Beutler-Fano profiles. At higher values of v2 the profiles become compressed in energy since dW/dv2 = l/vf. Fig. 19.2 shows two regular series of Beutler-Fano profiles between the Ba+ 6p1/2 and 6p3/2 limits. In this case the absorption never vanishes because there is more than one continuum. 

Most of the experiments to date have been carried out on doubly excited states converging to isolated low angular momentum states of the ion. In general the spectra are well characterized as two photon ICE spectra in which the observed spectrum is characterized by the product of an overlap integral and the spectral density of the doubly excited autoionizing states. As an example we show in Fig. 23.9 the Ba 6sl9d— 9dn d spectra observed by Camus et al.31 As shown in Fig. 

The differential cross section of a transition into a continuous spectrum can be also expressed in terms of generalized oscillator strengths. However, in this case we must introduce the spectral density of generalized oscillator strengths df q) =/( , g)113 14 ... 

This result suggests, if it is assumed that a C-H heteronuclear dipolar relaxation mechanism is operative, that methyl protons dominate the relaxation behavior of these carbons over much of the temperature range studied despite the 1/r dependence of the mechanism. The shorter T] for the CH as compared to the CH2 then arises from the shorter C-H distances. Apparently, the contributions to spectral density in the MHz region of the frequency spectrum due to backbone motions is minor relative to the sidegroup motion. The T p data for the CH and CH2 carbons also give an indication of methyl group rotational frequencies. 

So far, we have fairly extensively discussed the general aspects of static and dynamic relaxation of core holes. We have also discussed in detail methods for calculating the selfenergy (E). Knowing the self-energy, we know the spectral density of states function A (E) (Eq. (10)) which describes the X-ray photoelectron spectrum (XPS) in the sudden limit of very high photoelectron kinetic energy (Eq. (6)). We will now present numerical results for i(E) and Aj(E) and compare these with experimental XPS spectra and we will find many situations where atomic core holes behave in very unconventional ways. 

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