Connected Correlation Functions

Thus the correlation function connects between the solvation Helmholtz energy on the first site and on the second site. This is formally the same relation as we encountered several times in Chapter 3. Equation (6.14.7) can also be read as... 

There are two approaches connnonly used to derive an analytical connection between g(i-) and u(r) the Percus-Yevick (PY) equation and the hypemetted chain (FfNC) equation. Both are derived from attempts to fomi fimctional Taylor expansions of different correlation fimctions. These auxiliary correlation functions include ... 

Since the stochastic Langevin force mimics collisions among solvent molecules and the biomolecule (the solute), the characteristic vibrational frequencies of a molecule in vacuum are dampened. In particular, the low-frequency vibrational modes are overdamped, and various correlation functions are smoothed (see Case [35] for a review and further references). The magnitude of such disturbances with respect to Newtonian behavior depends on 7, as can be seen from Fig. 8 showing computed spectral densities of the protein BPTI for three 7 values. Overall, this effect can certainly alter the dynamics of a system, and it remains to study these consequences in connection with biomolecular dynamics. 

Then, performing a disorder average in Eq. (19), and using Eq. (18) we can obtain the following two relations for the connected and blocking correlation functions... 

The equlibrium between the bulk fluid and fluid adsorbed in disordered porous media must be discussed at fixed chemical potential. Evaluation of the chemical potential for adsorbed fluid is a key issue for the adsorption isotherms, in studying the phase diagram of adsorbed fluid, and for performing comparisons of the structure of a fluid in media of different microporosity. At present, one of the popular tools to obtain the chemical potentials is an approach proposed by Ford and Glandt [23]. From the detailed analysis of the cluster expansions, these authors have concluded that the derivative of the excess chemical potential with respect to the fluid density equals the connected part of the fluid-fluid direct correlation function (dcf). Then, it follows that the chemical potential of a fluid adsorbed in a disordered matrix, p ), is... 

The above results show that the structure of the system with the molecules self-assembled into the internal films is determined by their correlation functions. In contrast to simple fluids, the four-point correlation functions are as important as the two-point correlation functions for the description of the structure in this case. The oil or water domain size is related to the period of oscillations A of the two-point functions. The connectivity of the oil and water domains, related to the sign of K, is determined by the way four moleeules at distanees eomparable to their sizes are eorrelated. For > 0 surfactant molecules are correlated in such a way that preferred orientations... 

Perdew and Wang have proposed an exchange functional similar to B88 to be used in connection with the PW91 correlation functional given below (eq. (6.30)). 

Here u is a unit vector oriented along the rotational symmetry axis, while in a spherical molecule it is an arbitrary vector rigidly connected to the molecular frame. The scalar product u(t) (0) is cos 0(t) in classical theory, where 6(t) is the angle of u reorientation with respect to its initial position. It can be easily seen that both orientational correlation functions are the average values of the corresponding Legendre polynomials ... 

Multiplying (2.22) by (— l)q d q 0) and summing over q according to (2.11), we obtain an equation that connects the correlation functions of the perturbation to those of the response ... 

Starting with a crude model of a polymer melt, consisting of anharmonic springs connecting repulsive beads, with a bending potential to represent the polymer stiffness, the authors show how the time correlation function, C(f), should be expected to behave as a function of the polymer stiffness. 

To complete the description and get the connection with the solute emission and absorption spectra, there is need of the correlation functions of the dipole operator pj= (a(t)+af(t))j and, consequently, the differential equation for the one solute mode has to be solved. The reader is referred to [133] for detailed analysis of this point as well as the equations controlling the relaxation to equilibrium population. The energy absorption and emission properties of the above model are determined by the two-time correlation functions ... 

This simple model of rigid rods connected by Hookean torsion springs has been criticized as unrealistic, because it does not reflect the atomic structure of a real DNA. However, this objection misses an essential point, namely, that the correlation functions obtained for this simple model are also valid for a much wider class of models over the observable time domain. The reason is as follows. The earliest time at which depolarization due to twisting can be distinguished from wobble is about 0.5 ns/39-87) The wavelength of the... 

Different equilibrium, hydrodynamic, and dynamic properties are subsequently obtained. Thus, the time-correlation function of the stress tensor (corresponding to any crossed-coordinates component of the stress tensor) is obtained as a sum over all the exponential decays of the Rouse modes. Similarly, M[rj] is shown to be proportional to the sum of all the Rouse relaxation times. In the ZK formulation [83], the connectivity matrix A is built to describe a uniform star chain. An (f-l)-fold degeneration is found in this case for the f-inde-pendent odd modes. Viscosity results from the ZK method have been described already in the present text. 

At this point we again stress the sequence of definitions leading to Eq. (4.2.16). First, the correlation function is defined as a measure of the extent of the dependence between the two events in Eq. (4.2.12) [or, equivalently, in Eq. (4.2.13)]. The probabilities used in the definition of g a, b) were read from the GPF of the system, e.g., (4.2.1). This side of g a, b) allows us to investigate the molecular content of the correlation function, which is the central issue of this book. The other side of g a, b) follows from the recognition that the limiting value of g(a, b), denoted by g a, b), connects the binding constants ah and kg A. This side of g a, b) allows us to extract information on the cooperativity of the system from the experimental data. In other words, these relationships may be used to calculate the correlation fimction from experimental data, on the one hand, and to interpret these correlation functions in terms of molecular properties, on the other. 

With the availability of lasers, Brillouin scattering can now be used more confidently to study electron-phonon interactions and to probe the energy, damping and relative weight of the various hydro-dynamic collective modes in anharmonic insulating crystals.The connection between the intensity and spectral distribution of scattered light and the nuclear displacement-displacement correlation function has been extensively discussed by Griffin 236). 

Usually, experimentalists quantify step fluctuations by averaging the data to find the correlation function G(t) = 0.5 < (h(x,i) - h(x,0)Y >, where h x,t) specifies the step position at time t and the average is over many sample points, x. G(f) measures how far a position on a step wanders with time. If that position were completely free to wander, it would obey a diffusive law G(t) t. However, its motion is restricted by the fact that it is connected to the other parts of the step. For that reason G(t) is sub-diffusive. The detailed law which G(f) obeys is dependent on the atomic processes which mediate step motion. For example, if the step edge is able to freely exchange... 

Time-dependent correlation functions are now widely used to provide concise statements of the miscroscopic meaning of a variety of experimental results. These connections between microscopically defined time-dependent correlation functions and macroscopic experiments are usually expressed through spectral densities, which are the Fourier transforms of correlation functions. For example, transport coefficients1 of electrical conductivity, diffusion, viscosity, and heat conductivity can be written as spectral densities of appropriate correlation functions. Likewise, spectral line shapes in absorption, Raman light scattering, neutron scattering, and nuclear jmagnetic resonance are related to appropriate microscopic spectral densities.2... 

The definition of the spectral density [Eq. (15)] allows to connect the various correlation functions relevant to spectral broadening and spectral diffusion. For example, the fluorescence Stokes shift function S(t) can be written as... 

The previous discussion shows that the relaxation processes emerge from the quantum dynamics under appropriate circumstances leading to the formation of time-dependent quasiclassical parts in the observable quantities. Let us add that quasiclassical and semiclassical methods have been recently applied to the optical response of quantum systems in several works [65, 66] where the relation to the Liouville formulation of quantum mechanics has been discussed, without however pointing out the existence of Liouvillian resonances as we discussed here above. The connection between the property of chaos and n-time correlation functions or the nth-order response of a system in multiple-pulse experiments has also been discussed [67, 68]. 

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