Field autocorrelation function

The same idea was actually exploited by Neumann in several papers on dielectric properties [52, 69, 70]. Using a tin-foil reaction field the relation between the (frequency-dependent) relative dielectric constant e(tj) and the autocorrelation function of the total dipole moment M t] becomes particularly simple ... 

I will present here the properties of various sources when the random variable considered is the field intensity. In this case, one has access to the mean and variance via a simple photodetector. The autocorrelation function can be interpreted as the probability of detecting one photon at time t + t when one photon has been detected at time t. The measurement is done using a pair of photodetectors in a start stop arrangement (Kimble et al., 1977). The system is usually considered stationary so that the autocorrelation function, which is denoted depends only on r and is defined by ... 

Finally, the field autocorrelation function is constant equal to 1. 

A Fock state is a state containing a fixed number of photons, N. These states are very hard to produce experimentally for A > 2. Their photon number probability density distribution P (m) is zero everywhere except for m = N, their variance is equal to zero since the intensity is perfectly determined. Finally, the field autocorrelation function is constant... 

The different behaviors for the field autocorrelation function are summarized on Fig. 1. 

Raman intensities of the molecular vibrations as well as of their crystal components have been calculated by means of a bond polarizibility model based on two different intramolecular force fields ([87], the UBFF after Scott et al. [78] and the GVFF after Eysel [83]). Vibrational spectra have also been calculated using velocity autocorrelation functions in MD simulations with respect to the symmetry of intramolecular vibrations [82]. 

Figure 10 Polarized field autocorrelation function g(1) for poly(p-phenylene)...

DLS is a versatile experimental technique, which is readily available in many laboratories. As discussed in Section 5.2, the field autocorrelation function g (r)... 

The linear response theory [50,51] provides us with an adequate framework in order to study the dynamics of the hydrogen bond because it allows us to account for relaxational mechanisms. If one assumes that the time-dependent electrical field is weak, such that its interaction with the stretching vibration X-H Y may be treated perturbatively to first order, linearly with respect to the electrical field, then the IR spectral density may be obtained by the Fourier transform of the autocorrelation function G(t) of the dipole moment operator of the X-H bond ... 

NMR 13C spin-lattice relaxation times are sensitive to the reorientational dynamics of 13C-1H vectors. The motion of the attached proton(s) causes fluctuations in the magnetic field at the 13C nuclei, which results in decay of their magnetization. Although the time scale for the experimentally measured decay of the magnetization of a 13C nucleus in a polymer melt is typically on the order of seconds, the corresponding decay of the 13C-1H vector autocorrelation function is on the order of nanoseconds, and, hence, is amenable to simulation. 

This effective Q,t-range overlaps with that of DLS. DLS measures the dynamics of density or concentration fluctuations by autocorrelation of the scattered laser light intensity in time. The intensity fluctuations result from a change of the random interference pattern (speckle) from a small observation volume. The size of the observation volume and the width of the detector opening determine the contrast factor C of the fluctuations (coherence factor). The normalized intensity autocorrelation function g Q,t) relates to the field amplitude correlation function g (Q,t) in a simple way g t)=l+C g t) if Gaussian statistics holds [30]. g Q,t) represents the correlation function of the fluctuat-... 

Abbreviations MD, molecular dynamics TST, transition state theory EM, energy minimization MSD, mean square displacement PFG-NMR, pulsed field gradient nuclear magnetic resonance VAF, velocity autocorrelation function RDF, radial distribution function MEP, minimum energy path MC, Monte Carlo GC-MC, grand canonical Monte Carlo CB-MC, configurational-bias Monte Carlo MM, molecular mechanics QM, quantum mechanics FLF, Hartree-Fock DFT, density functional theory BSSE, basis set superposition error DME, dimethyl ether MTG, methanol to gasoline. 

The dipole autocorrelation function is the expectation value over the equilibrium ensemble of an unperturbed system of atoms or molecules (i.e., without an applied field),... 

It is not surprising that the autocorrelation function involves the field as felt by the particle while it moves with the unperturbed velocity v. 

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,... 

Here <( t ) f(t")> is the autocorrelation function of the electromagnetic field. For the case of excitation by a conventional light source, where the amplitudes and the phases of the field are subject to random fluctuations, the field autocorrelation function differs from zero for time intervals shorter than the reciprocal width of the exciting source. In the limit 8v A, that is when the spectral width, 8v, of the source exceeds the inhomogenously broadened line width, the field autocorrelation function can be represented as a delta function... 

For a theoretical calculation of relaxation times one. must write the temporal autocorrelation functions of several functions Fn of the interparticle coordinates riS(t), 0y(O, and interparticle distance and where 0,/O and external magnetic field Ho (here particle refers to magnetic nuclei and atoms). The relaxation rates are proportional to the Fourier intensities of these autocorrelation functions at selected frequencies. For example, Torrey (16) has written for this autocorrelation function the equivalent ensemble average... 

In this section it will be outlined how the different molar masses contribute to the TDFRS signal. Of especial interest is the possibility of selective excitation and the preparation of different nonequilibrium states, which allows for a tuning of the relative statistical weights in the way a TDFRS experiment is conducted. Especially when compared to PCS, whose electric field autocorrelation function g t) strongly overestimates high molar mass contributions, a much more uniform contribution of the different molar masses to the heterodyne TDFRS diffraction efficiency t) is found. This will allow for the measurement of small... 

The normalized electric field autocorrelation function gift), which can be calculated from the normalized intensity autocorrelation function g2(t) = (1(0) 7(f)) (I(0)/2 according to the Siegert relation [56]... 

Fig. 15.8. Schematic one-dimensional illustration of electronic predissociation. The photon is assumed to excite simultaneously both excited states, leading to a structureless absorption spectrum for state 1 and a discrete spectrum for state 2, provided there is no coupling between these states. The resultant is a broad spectrum with sharp superimposed spikes. However, if state 2 is coupled to the dissociative state, the discrete absorption lines turn into resonances with lineshapes that depend on the strength of the coupling between the two excited electronic states. Two examples are schematically drawn on the right-hand side (weak and strong coupling). Due to interference between the non-resonant and the resonant contributions to the spectrum the resonance lineshapes can have a more complicated appearance than shown here (Lefebvre-Brion and Field 1986 ch.6). In the first case, the autocorrelation function S(t) shows a long sequence of recurrences, while in the second case only a single recurrence with small amplitude is developed. The diffuseness of the resonances or vibrational structures is a direct measure of the electronic coupling strength.

The intensity distribution of particle size, G(a), is related to the experimentally observed electric field autocorrelation function, g[Pg.107]

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