Quantum information‐theoretic measures for the static screened Coulomb potential

In this research work, the quantum information‐theoretic analysis of the static screened Coulomb potential has been carried out by studying both analytically and numerically the entropic measures, Fisher information as well as the Onicescu information energy of its wave function. Explicit expressions of these information‐theoretic measures were obtained. Using the Srivastava–Daoust linearization formula in terms of the multivariate Lauricella hypergeometric function, the Rényi entropy, Tsallis entropy, Onicescu information energy were analytically obtained. From the results obtained, it is observed that some of the Shannon entropies are negative, indicating that, negative entropies exists for the probability densities that are highly localized. The trends in the variation of the information‐theoretic measures with the potential screening parameter a for this atomic model are discussed. The Bialynicki‐Birula, Mycielski inequality (BBM), and the Fisher information based uncertainty relation are also verified.     

Two-dimensional confined hydrogen: An entropy and complexity approach

The position and momentum spreading of the electron distribution of the two-dimensional confined hydrogenic atom, which is a basic prototype of the general multidimensional confined quantum systems, is numerically studied in terms of the confinement radius for the 1s, 2s, 2p, and 3d quantum states by means of the main entropy and complexity information-theoretical measures. First, the Shannon entropy and the Fisher information, as well as the associated uncertainty relations, are computed and discussed. Then, the Fisher-Shannon, lopezruiz-mancini-alvet, and LMC-Rényi complexity measures are examined and mutually compared. We have found that these entropy and complexity quantities reflect the rich properties of the electron confinement extent in the two conjugated spaces.     

Benchmark values of Shannon entropy for spherically confined hydrogen atom

The information‐theoretic measure of confined hydrogen atom has been investigated extensively in the literature. However, most of them were focused on the ground state and accurate values of information entropies, such as Shannon entropy, for confined hydrogen are still not determined. In this work, we establish the benchmark results of the Shannon entropy for confined hydrogen atom in a spherical impenetrable sphere, in both position and momentum spaces. This is done by examining the bound state energies, the normalization of wave functions, and the scaling property with respect to isoelectronic hydrogenic ions. The angular and radial parts of Shannon entropy in two conjugate spaces are provided in detail for both free and confined hydrogen atom in ground and several excited states. The entropies in position space decrease logarithmically with decreasing the size of confinement, while those in momentum space increase logarithmically. The Shannon entropy sum, however, approaches to finite values when the confinement radius closes to zero. It is also found that the Shannon entropy sum shares same trend for states with similar density distributions. Variations of entropy for nodeless bound states are significantly distinct form those owning nodes when changing the confinement radius.     

密度泛函活性理论中的Rényi熵, Tsallis熵和Onicescu信息能

根据密度泛函理论,分子的电子密度确定了该体系基态下的所有性质,其中包括结构和反应活性.如何运用电子密度泛函有效地预测分子反应活性仍然是一个有待解决的难题.密度泛函活性理论(DFRT)倾力打造这样一个理论和概念架构,使得运用电子密度以及相关变量准确地预测分子的反应特性成为可能.信息理论方法的香农熵和费舍尔信息就是这样的密度泛函,研究表明,它们均可作为反应活性的有效描述符.本文将在DFRT框架中介绍和引进三个密切相关的描述符, Rényi熵、Tsallis熵和Onicescu信息能.我们准确地计算了它们在一些中性原子和分子中的数值并讨论了它们随电子数量和电子总能量的变化规律.此外,以第二阶Onicescu信息能为例,在分子和分子中的原子两个层面上,系统地考察了其随乙烷二面角旋转的变化模式.这些新慨念的引入将为我们深入洞察和预测分子的结构和反应活性提供额外的描述工具.     

Shannon-information entropy sum in the confined hydrogenic atom

The appearance of critical points in the Shannon entropy sum as a function of confinement radius, in ground and excited state confined hydrogenic systems, is discussed. We illustrate that the Coulomb potential in tandem with the hard sphere confinement are responsible for these points. The positions of these points are observed to vary with the intensity of the potential. The effects of the Coulomb potential on the system are further probed, by examining the differences between the densities of the confined atom and those of the particle confined in a spherical box, for the same confinement radius. These differences are quantified by using Kullback-Leibler and cumulative residual Kullback-Leibler distance measures from information theory. These measures detect that the effects of the Coulomb potential are squeezed out of the system as the confinement radius decreases. That is, the confined atom densities resemble the particle in a box ones, for smaller confinement radii. Furthermore, the critical points in the entropy sum lie in the same regions where there are changes in the distance measures, as the atom behaves more particle in a spherical box-like. The analysis is further complemented by examination of the derivative of the entropy sum with respect to confinement radius. This study illustrates the inhomogeneity in the magnitudes of the derivatives of the entropy sum components and their dependence on the Coulomb potential. A link between the derivative and the entropic force is also illustrated and discussed. Similar behaviors are observed when the virial ratio is compared to the entropic power one, as a function of confinement radius.     

The confined helium atom: An information–theoretic approach

In this article, we study the helium atom confined in a spherical impenetrable cavity by using informational measures. We use the Ritz variational method to obtain the energies and wave functions of the confined helium atom as a function of the cavity radius $r_0$. As trial wave functions we use one uncorrelated function and five explicitly correlated basis sets in Hylleraas coordinates with different degrees of electronic correlation. We computed the Shannon entropy, Fisher information, Kullback–Leibler entropy, Tsallis entropy, disequilibrium and Fisher–Shannon complexity, as a function of $r_0$. We found that these entropic measures are sensitive to electronic correlation and can be used to measure it. As expected these entropic measures are less sensitive to electron correlation in the strong confinement regime ( a.u.).     

Accurate energy eigenvalues and eigenfunctions for the two‐dimensional confined hydrogen atom

A study of the two‐dimensional hydrogen atom confined within a circle of impenetrable walls is presented. The potential inside the box is Coulomb type, whereas outside it is infinite. The energy eigenvalues and some radial wave function properties are computed with high accuracy for different box sizes. We derive the polarizability in the Kirkwood approximation, calculate the Fermi contact term as a function of the confinement radius, and investigate the filling order of the one‐electron states. When the electronic configuration of many electrons is constructed by means of the Aufbau principle, the model predicts the inversion 2s–3d levels in the N atom. © 2005 Wiley Periodicals, Inc. Int J Quantum Chem, 2005     

Entropic measures of Rydberg‐like harmonic states

The Shannon entropy, the desequilibrium and their generalizations (Rényi and Tsallis entropies) of the three‐dimensional single‐particle systems in a spherically symmetric potential V(r) can be decomposed into angular and radial parts. The radial part depends on the analytical form of the potential, but the angular part does not. In this article, we first calculate the angular entropy of any central potential by means of two analytical procedures. Then, we explicitly find the dominant term of the radial entropy for the highly energetic (i.e., Rydberg) stationary states of the oscillator‐like systems. The angular and radial contributions to these entropic measures are analytically expressed in terms of the quantum numbers which characterize the corresponding quantum states and, for the radial part, the oscillator strength. In the latter case, we use some recent powerful results of the information theory of the Laguerre polynomials and spherical harmonics which control the oscillator‐like wavefunctions.     

Shannon entropy as a predictor of avoided crossing in confined atoms

Avoided crossing is one of the unique spectroscopic features of a confined atomic system. Shannon information entropy of the ground state and some of the excited states of confined H atom as a predictor of avoided crossing is studied in this work. This is accomplished by varying the strength of the confinement and examining structure properties like ionization energy and Shannon information entropy. Along with the energy level repulsion at the avoided crossing, Shannon information entropy is also exchanged between the involved states. This work also addresses a question: In addition to that regarding localization, what other property of the system can be extracted from Shannon entropy? Insightful connection is discovered between Shannon entropy and the average value of confinement potential, Coulomb potential, and kinetic energy.     

Study of a confined hydrogen‐like atom by the asymptotic iteration method

The asymptotic iteration method (AIM) is used to obtain both special exact solutions and general approximate solutions for a Hydrogen‐like atom confined in a spherical box of arbitrary radius R. Critical box radii, at which states are no longer bound, are also calculated. The results are compared with those in the literature. © 2008 Wiley Periodicals, Inc. Int J Quantum Chem, 2009     

Net information measures for modified Yukawa and Hulthén potentials

The dimensional analyses of the position and momentum variances‐based quantum mechanical Heisenberg uncertainty measure, as well as the entropic information measures given by the Shannon information entropy sum and the product of Fisher information measures are carried out for two widely used nonrelativistic isotropic exponential‐cosine screened Coulomb potentials generated by multiplying the superpositions of (i) Yukawa‐like, ?Z(e^?μr/r), and (ii) Hulthén‐like, ?Zμ(1/(e^μr ? 1)), potentials by cos(bμr) followed by addition of the term a/r², where a and b ≥ 0, μ are the screening parameters and Z, in case of atoms, denotes the nuclear charge. Under the spherical symmetry, all the information measures considered are shown to be independent of the scaling of the set [μ, Z] at a fixed value of μ/Z, a, and b and the other parameters defining the superpositions of the potentials. Numerical results are presented, which support the validity of the scaling properties. © 2007 Wiley Periodicals, Inc. Int J Quantum Chem, 2007     

Fine structure in the hydrogen atom boxed in a spherical impenetrable cavity

The spectrum of the hydrogen atom confined in a spherical impenetrable box of radius R_c has been investigated by many authors up to date, but not at the level of relativistic corrections. It is well known that, as R_c diminishes, all energy levels and the pressure increase very rapidly, whereas the polarizability goes to zero. In this report, we have computed the relativistic corrections that underlie the fine structure of the confined hydrogen atom, as a function of R_c. Such corrections correspond to relativistic kinetic energy, spin‐orbit coupling and the Darwin term, which are calculated in the frame of time‐independent perturbation theory, for which, use was made of the exact confined hydrogen atom wave functions. We show that for a confinement radius of 0.5 au the relativistic corrections increase up to three orders of magnitude with respect to those corresponding to the free atom. As R_c decreases, the kinetic energy correction and the spin‐orbit coupling for become negative whereas their absolute value and the Darwin term, which is positive, increase very rapidly.     

Hierarchical atom type definitions and extensible all‐atom force fields

The extensibility of force field is a key to solve the missing parameter problem commonly found in force field applications. The extensibility of conventional force fields is traditionally managed in the parameterization procedure, which becomes impractical as the coverage of the force field increases above a threshold. A hierarchical atom‐type definition (HAD) scheme is proposed to make extensible atom type definitions, which ensures that the force field developed based on the definitions are extensible. To demonstrate how HAD works and to prepare a foundation for future developments, two general force fields based on AMBER and DFF functional forms are parameterized for common organic molecules. The force field parameters are derived from the same set of quantum mechanical data and experimental liquid data using an automated parameterization tool, and validated by calculating molecular and liquid properties. The hydration free energies are calculated successfully by introducing a polarization scaling factor to the dispersion term between the solvent and solute molecules. © 2015 Wiley Periodicals, Inc.     

Electron‐density delocalization in many‐electron atoms confined by penetrable walls: A Hartree–Fock study

The electronic structure of several many‐electron atoms, confined within a penetrable spherical box, was studied using the Hartree–Fock (HF) method, coupling the Roothaan's approach with a new basis set to solve the corresponding one‐electron equations. The resulting HF wave‐function was employed to evaluate the Shannon entropy, , in configuration space. Confinements imposed by impenetrable walls induce decrements on when the confinement radius, R_c, is reduced and the electron‐density is localized. For confinements commanded by penetrable walls, exhibits an entirely different behavior, because when an atom starts to be confined, delivers values less than those observed for the free system, in the same way that the results presented by impenetrable walls. However, from a confinement radius, shows increments, and precisely in these regions, the spatial restrictions spread to the electron density. Thus, from results presented in this work, the Shannon entropy can be used as a tool to measure the electron density delocalization for many‐electron atoms, as the hydrogen atom confined in similar conditions.     

Entropic functionals of Laguerre polynomials and complexity properties of the half‐line Coulomb potential

The stationary states of the half‐line Coulomb potential are described by quantum‐mechanical wavefunctions, which are controlled by the Laguerre polynomials L(x). Here, we first calculate the qth‐order frequency or entropic moments of this quantum system, which is controlled by some entropic functionals of the Laguerre polynomials. These functionals are shown to be equal to a Lauricella function F(${1 \over q}$ ,…,,${1 \over q}$ ,1) by use of the Srivastava‐Niukkanen linearization relation of Laguerre polynomials. The resulting general expressions are applied to obtain the following information‐theoretic quantities of the half‐line Coulomb potential: disequilibrium, Renyi and Tsallis entropies. An alternative and simpler expression for the linear entropy is also found by means of a different method. Then, the Shannon entropy and the LMC shape complexity of the lowest and highest (Rydberg) energetic states are explicitly given; moreover, sharp information‐theoretic‐based upper bounds to these quantities are found for general physical states. These quantities are numerically discussed for the ground and various excited states. Finally, the uncertainty measures of the half‐line Coulomb potential given by the information‐theoretic lengths are discussed. © 2010 Wiley Periodicals, Inc. Int J Quantum Chem, 2011     

Correlation energy,correlated electron density,and exchange‐correlation potential in some spherically confined atoms

We report correlation energies, electron densities, and exchange‐correlation potentials obtained from configuration interaction and density functional calculations on spherically confined He, Be, Be²⁺, and Ne atoms. The variation of the correlation energy with the confinement radius R_c is relatively small for the He, Be²⁺, and Ne systems. Curiously, the Lee–Yang–Parr (LYP) functional works well for weak confinements but fails completely for small R_c. However, in the neutral beryllium atom the CI correlation energy increases markedly with decreasing R_c. This effect is less pronounced at the density‐functional theory level. The LYP functional performs very well for the unconfined Be atom, but fails badly for small R_c. The standard exchange‐correlation potentials exhibit significant deviation from the “exact” potential obtained by inversion of Kohn–Sham equation. The LYP correlation potential behaves erratically at strong confinements. © 2016 Wiley Periodicals, Inc.