Time-dependent electron localization function

The time-dependent density functional theory [38] for electronic systems is usually implemented at adiabatic local density approximation (ALDA) when density and single-particle potential are supposed to vary slowly both in time and space. Last years, the current-dependent Kohn-Sham functionals with a current density as a basic variable were introduced to treat the collective motion beyond ALDA (see e.g. [13]). These functionals are robust for a time-dependent linear response problem where the ordinary density functionals become strongly nonlocal. The theory is reformulated in terms of a vector potential for exchange and correlations, depending on the induced current density. So, T-odd variables appear in electronic functionals as well. 

The frequency dependence of SHG at simple metal surface has been the focus of a recent theoretical study of Liebsch [100]. Time-dependent density functional theory was used in these calculations. The results suggest that the perpendicular surface contribution to the second harmonic current is found to be significantly larger than had been assumed previously. He also concludes that for 2 a> close to the threshold for electron emission, the self-consistently screened nonlinear electronic response becomes resonantly enhanced, analogous to local field enhancement in the linear response near the bulk plasma frequency. 

The effective Time Dependent Kohn-Sham (TDKS) potential vks p (r>0 is decomposed into several pieces. The external source field vext(r,0 characterizes the excitation mechanism, namely the electromagentic pulse as delivered by a by passing ion or a laser pulse. The term vlon(r,/) accounts for the effect of ions on electrons (the time dependence reflects here the fact that ions are allowed to move). Finally, appear the Coulomb (direct part) potential of the total electron density p, and the exchange correlation potential vxc[p](r,/). The latter xc potential is expressed as a functional of the electronic density, which is at the heart of the DFT description. In practice, the functional form of the potential has to be approximated. The simplest choice consists in the Time Dependent Local Density Approximation (TDLDA). This latter approximation approximation to express vxc[p(r, /)]... 

Spin relaxation in a nucleus is induced by random fluctuations of local magnetic fields. These result from time-dependent modulation of the coupling energy of the resonating nuclear spin with nearby nuclear spins, electron spins, quadrupole moments, etc. Any time-dependent phenomenon able to modulate these couplings can contribute to nuclear relaxation. The distribution of the frequencies contained in these time-dependent phenomena is described by a correlation function, characterized by a parameter Tc, the correlation time. Its reciprocal can be considered as the maximum frequency produced by the fluctuations in the vicinity of the nuclear spin. If more than one process modulates the coupling between the nuclear spin and its surroundings, the reciprocal of the effective correlation time is the sum of the reciprocals of the various contributions... 

For multi-electron systems, it is not feasible, except possibly in the case of helium, to solve the exact atom-laser problem in 3 -dimensional space, where n is the number of electrons. One might consider using time-dependent Hartree Fock (TDHF) or the time-dependent local density approximation to represent the state of the system. These approaches lead to at least njl coupled equations in 3-dimensional space which is much more attractive computationally. For example, in TDHF the wave function for a closed shell system can be approximated by a single Slater determinant of time dependent orbitals,... 

The structure, however, is not static but is subject to thermally driven fluctuations. The local structure changes continuously as a function of time due to orientational and translational molecular motions. The time scale of these motions may range from nanoseconds up to several hundred years. The structure of the amorphous state as well as its time-dependent fluctuations can be analysed by various scattering techniques, such as X-ray, neutron, electron and light scattering. 

Note that here and later on r denotes the single-particle coordinate whereas R is still used as abbreviation for all nuclear positions as in Eq. (1). The potential (5) consists, on one hand, of an external potential V(r,R), which in our case is time-dependent owing to the atomic motion R( ). On the other hand, there are electron-electron interaction terms, namely the Hartree and the exchange-correlation term, which depend both via the density p on the functions tpj. The exchange-correlation potential VIC is defined within the so-called adiabatic local density approximation [25] which is the natural extension of the lda from stationary dpt. It is assumed to give reliable results for problems where the time scale of the external potential (in our case typical collision times) is larger than the electronic time scale. 

Popular qualitative chemical concepts such as electronegativity [1] and hardness [2] have been widely used in understanding various aspects of chemical reactivity. A rigorous theoretical basis for these concepts has been provided by density functional theory (DFT). These reactivity indices are better appreciated in terms of the associated electronic structure principles such as electronegativity equalization principle (EEP), hard-soft acid-base principle, maximum hardness principle, minimum polarizability principle (MPP), etc. Local reactivity descriptors such as density, Fukui function, local softness, etc., have been used successfully in the studies of site selectivity in a molecule. Local variants of the structure principles have also been proposed. The importance of these structure principles in the study of different facets of medicinal chemistry has been highlighted. Because chemical reactions are actually dynamic processes, time-dependent profiles of these reactivity descriptors and the dynamic counterparts of the structure principles have been made use of in order to follow a chemical reaction from start to finish. 

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