Autocorrelation function method

In principle, we can evaluate Os if by direct counting of collision and reflection events from the molecidar trajectory data for both cases, we observed sufficient number (about 200) of collision events. To estimate Os,.if quantitatively, we have developed an autocorrelation function method. The result is Oseif —90% and there is no qualitative difference among various types of fluids, which suggests that the condensation as a unimolecular chemical reaction is a barricrless process. Calcidation of the local chemical potential also supports this barrieijess picture. ... 

In an ambitious study, the AIMS method was used to calculate the absorption and resonance Raman spectra of ethylene [221]. In this, sets starting with 10 functions were calculated. To cope with the huge resources required for these calculations the code was parallelized. The spectra, obtained from the autocorrelation function, compare well with the experimental ones. It was also found that the non-adiabatic processes described above do not influence the spectra, as their profiles are formed in the time before the packet reaches the intersection, that is, the observed dynamic is dominated by the torsional motion. Calculations using the Condon approximation were also compared to calculations implicitly including the transition dipole, and little difference was seen. 

Fluorescence intensity detected with a confocal microscope for the small area of diluted solution temporally fluctuates in sync with (i) motions of solute molecules going in/out of the confocal volume, (ii) intersystem crossing in the solute, and (hi) quenching by molecular interactions. The degree of fluctuation is also dependent on the number of dye molecules in the confocal area (concentration) with an increase in the concentration of the dye, the degree of fluctuation decreases. The autocorrelation function (ACF) of the time profile of the fluorescence fluctuation provides quantitative information on the dynamics of molecules. This method of measurement is well known as fluorescence correlation spectroscopy (FCS) [8, 9]. 

In addition to the fact that MPC dynamics is both simple and efficient to simulate, one of its main advantages is that the transport properties that characterize the behavior of the macroscopic laws may be computed. Furthermore, the macroscopic evolution equations can be derived from the full phase space Markov chain formulation. Such derivations have been carried out to obtain the full set of hydrodynamic equations for a one-component fluid [15, 18] and the reaction-diffusion equation for a reacting mixture [17]. In order to simplify the presentation and yet illustrate the methods that are used to carry out such derivations, we restrict our considerations to the simpler case of the derivation of the diffusion equation for a test particle in the fluid. The methods used to derive this equation and obtain the autocorrelation function expression for the diffusion coefficient are easily generalized to the full set of hydrodynamic equations. 

The Langevin dynamics method simulates the effect of individual solvent molecules through the noise W, which is assumed to be Gaussian. The friction coefficient r is related to the autocorrelation function of W through the fluctuation-dissipation theorem,... 

A semiclassical description is well established when both the Hamilton operator of the system and the quantity to be calculated have a well-defined classical analog. For example, there exist several semiclassical methods for calculating the vibrational autocorrelation function on a single excited electronic surface, the Fourier transform of which yields the Franck-Condon spectmm [108, 109, 150, 244]. In particular, semiclassical methods based on the initial-value representation of the semiclassical propagator [104-111, 245-248], which circumvent the cumbersome root-search problem in boundary-value-based semiclassical methods, have been successfully applied to a variety of systems (see, for example, Refs. 110, 111, 161, and 249 and references therein). The mapping procedure introduced in Section VI results in a quantum-mechanical Hamiltonian with a well-defined classical limit, and therefore it... 

To illustrate the potential of the hybrid method in describing the role of an intramolecular bath in the decay dynamics induced by a conical intersection, we consider the model of Ref. [7,8] for the S2-S1 Cl in pyrazine. Fig. 1 shows the wavepacket autocorrelation function C(t) = ( k(O)l (t) for an increasing number of bath modes. G-MCTDH hybrid calculations for 4 core (primary) modes plus nb bath (secondary) modes are compared with reference calculations by the standard MCTDH method. 

Fig. 1. The autocorrelation function C(t) = (U (O)l I (i) is shown for a wavepacket initially prepared on the upper diabatic surface [7]. Panels (a) and (b) C(t) for the four core modes calculated by the standard MCTDH method for the model Hamiltonian Hy of Eq. (9), shown on different scales in the two panels. Panel (c) G-MCTDH calculation (bold line) as compared with standard MCTDH calculation (dotted line) for the composite system with four core modes (combined into two 2-dimensional particles

Fig. 4. Spectral density for the velocity autocorrelation function for vibrations of abody-centered cubic lattice, extrapolated from 7 even moments, by the method of Section IV.

Induced dipole autocorrelation functions of three-body systems have not yet been computed from first principles. Such work involves the solution of Schrodinger s equation of three interacting atoms. However, classical and semi-classical methods, especially molecular dynamics calculations, exist which offer some insight into three-body dynamics and interactions. Very useful expressions exist for the three-body spectral moments, with the lowest-order Wigner-Kirkwood quantum corrections which were discussed above. 

Density expansion. The method of cluster expansions has been used to obtain the time-dependent correlation functions for a mixture of atomic gases. The particle dynamics was treated quantum mechanically. Expressions up to third order in density were given explicitly [331]. We have discussed similar work in the previous Section and simply state that one may talk about binary, ternary, etc., dipole autocorrelation functions. 

Ternary and Other Induced Spectra. Three-particle induced dipoles and the associated ternary collision-induced absorption spectra and dipole autocorrelation functions have been studied for fluids composed of mixtures of rare gases, and for neat fluids of nonpolar molecules — that is for systems that are widely thought to interact with radiation only by virtue of interaction-induced properties. A convenient framework is thus obtained for understanding the variety of experimental observations. The computer simulation studies permit an insight into the involved basic processes, but were not intended for direct comparison with measurements [57]. Methods have been developed for computer... 

J. Manz The theoretical method of Prof. Field (See Field et al., Intramolecular Dynamics in the Frequency Domain, this volume.) evaluates the fluorescence dispersion spectra of HCCH in terms of the Fourier transform of the autocorrelation function,... 

The stochastic reconstruction method is based on the idea that an arbitrarily complex porous structure can be described by a binary phase function which assumes a value 0 in the pore space and 1 in the solid matrix29 The intrinsic randomness of the phase function can be adequately qualified by the low order statistical moments, namely porosity and two-point autocorrelation function.29 The porosity is the probability that a voxel is in the pore space. The two-point autocorrelation function is the probability that two... 

In our approach [1, 2] termed the dynamic method the complex susceptibility x = x — ix" is determined by a law of undamped motion of a dipole in a given potential well and by dissipation mechanism often described as stosszahlansatz in the underlying kinetic or Boltzmann equation. In this review we shall refer to this (dynamic) method as the ACF method, since it is actually based on calculation of the spectrum of the dipolar autocorrelation function (ACF). Actually we use a one-particle approximation, in which the form of an employed potential well (being in many cases rectangular or close to it) is taken a priori. Correlation of the particles coordinates is characterized implicitly by the Kirkwood correlation factor g, its value being taken from the experimental data. The ACF method is simple and effective, because we do not employ the stochastic equations of motions. This feature distinguishes our method from other well-known approaches—for example, from those described in books [13, 14]. 

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