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Physical Review A

Fisher-Shannon analysis of ionization processes and isoelectronic series

K. D. Sen, J. Antolín, Juan Carlos Angulo

Published Sep 12, 2007• 90 citations
Publisher

Abstract

The Fisher-Shannon plane which embodies the Fisher information measure in conjunction with the Shannon entropy is tested in its ability to quantify and compare the informational behavior of the process of atomic ionization. We report the variation of such an information measure and its constituents for a comprehensive set of neutral atoms, and their isoelectronic series including the mononegative ions, using the numerical data generated on 320 atomic systems in position, momentum, and product spaces at the Hartree-Fock level. It is found that the Fisher-Shannon plane clearly reveals shell-filling patterns across the periodic table. Compared to position space, a significantly higher resolution is exhibited in momentum space. Characteristic features in the Fisher-Shannon plane accompanying the ionization process are identified, and the physical reasons for the observed patterns are described.

DOI
10.1103/physreva.76.032502

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The Fisher-Shannon plane which embodies the Fisher information measure in conjunction with the Shannon entropy is tested in its ability to quantify and compare the informational behavior of the process of atomic ionization. We report the variation of such an information measure and its constituents for a comprehensive set of neutral atoms, and their isoelectronic series including the mononegative ions, using the numerical data generated on 320 atomic systems in position, momentum, and product spaces at the Hartree-Fock level. It is found that the Fisher-Shannon plane clearly reveals shell-filling patterns across the periodic table. Compared to position space, a significantly higher resolution is exhibited in momentum space. Characteristic features in the Fisher-Shannon plane accompanying the ionization process are identified, and the physical reasons for the observed patterns are described.
Fisher information is calculated for the ground state of He-isoelectronic series, in position ([Formula: see text]) space. The results are given and discussed as a function of the nuclear charge (Z) and the screening parameter (λ) in the case study of Yukawa potential. Simple and explicit one-, two-, and three-correlated terms of Hylleraas wave function are used to focus on extracting the most characteristic physical features of the results. The numerical values of Fisher information are given in 1- and 2-electron charge densities, and their ratio of 2- to 1-electron densities results are defined and analyzed. To enable a comparison with others, the Fisher–Shannon information products, which measure the electron–electron correlation strength, are calculated in 1-electron density. The calculations of Fisher information, the ratio, and the Shannon-information products for two-electron systems in the presence of Yukawa potential are carried out for the first time in this study.
Atomic information entropies are computed from configuration interaction wavefunctions for members of the lithium isoelectronic series. For each member of the series, a sequence of wavefunctions built from increasingly larger basis sets is generated which satisfies a density convergence criterion, and exhibits a monotonic behaviour with respect to the density generated from the wavefunctions. Studies of the behaviour of the entropies along a sequence for a particular atom includes trends which have been shown to be present at the Hartree-Fock level. Results suggest that the position and momentum entropies are sensitive to small changes in density and thus can be useful indicators of the quality of the density. The sum of the entropies is also shown to be a useful indicator when density differences are larger. The nature of the information entropy-energy relationship is examined.
This work presents analytical and numerical results for the position- and momentum-space information entropies, of the 1s 2 -state of helium-like ions, using different interaction potentials. The potentials that we used are the Yukawa potential (YP), and the exponential-cosine-screened Coulomb potential (ECSCP). The investigated studies allow us to relate the position-space information with the momentum-space information of Shannon and Fisher, as well as Shannon entropy power, and the Fisher-Shannon information product, through different famous relations. The calculation is done using the one-electron charge density of entangled two-parameter wave function. On one hand, the results that are presented for ten members in the helium isoelectronic sequence demonstrate with precision the effect of correlation on bare charge distributions. On the other hand, it leads to some very important results for both the correlated and uncorrelated values of the informatic entropies. Analytical formula for the momentum-space information entropies are given. The effect of the nuclear charge and the screening parameter on the information expressions has been studied for both potentials. Detailed computational and numerical values and characteristics of these information quantities, as a function of the screening parameter, are reported here for the first time. New inequality has been proposed with Fisher’s total value to measure the correlation of two electrons.
Discrete Shannon entropy was introduced in view of the mathematical properties of multiconfiguration methods and then used to interpret the information in atomic states expressed by the multiconfiguration Dirac-Hartree-Fock wavefunction for Ni-like isoelectronic sequence. Moreover, the relationship between the concepts, including sudden change of Shannon entropy, information exchange, eigenlevel anticrossing, and strong configuration interaction, was clarified by induction on the basis of the present calculation of the energy structure for Ni-like isoelectronic sequence. It was found that there is an interesting connection between the change of Shannon entropies and eigenlevel anticrossings, along with the nuclear charge Z, which is helpful to conveniently locate the position of eigenlevel anticrossings and information exchanging and understand them from the point of view of information, besides the traditional physical concepts. Especially, it is concluded that in a given configuration space eigenlevel anticrossing is a sufficient and necessary condition for the sudden change of Shannon entropy, which is also a sufficient condition for information exchange.
General model-independent relationships among radial expectation values of the one-particle densities in position and momentum spaces for any quantum-mechanical system are obtained. They are derived from the Stam uncertainty principle and the recently reported lower bounds to the Fisher information entropy of both densities. The results are usually expressed in terms of some uncertainty products of the system. The accuracy of the bounds is numerically analyzed for neutral atoms within a Hartree-Fock framework.
We present a comparative study of several information and statistical complexity measures in order to examine a possible correlation with certain experimental properties of atomic structure. Comparisons are also carried out quantitatively using Pearson correlation coefficient. In particular, we show that Fisher information in momentum space is very sensitive to shell effects, and is directly associated with some of the most characteristic atomic properties, such as atomic radius, ionization energy, electronegativity, and atomic dipole polarizability. Finally we present a relation that emerges between Fisher information and the second moment of the probability distribution in momentum space i.e. an energy functional of interest in (e,2e) experiments.