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Physical Review A

Electron structure of a dipole-bound anion confined in a spherical box

Shai Ronen

Published Jul 22, 2003• 7 citations
Publisher

Abstract

We propose a model describing the interaction of an electron confined in a spherical box with a polar molecule in the center of the box, including an inner repulsive potential. As a preparation to its investigation, we calculate the average radius of a dipole-bound nonconfined electron, for which a closed form expression is found. The angular dependence of the wave function is also discussed, with implications for the choice of basis functions for ab initio calculations. The Schr\"odinger equation in the spherical box is then solved. The negative energy eigenstates of the system and the dependence of the ground-state energy on the radius of the confining sphere are obtained. Interestingly, a very simple expression is found for the total number of negative energy levels for a given dipole strength and confining sphere radius.

DOI
10.1103/physreva.68.012106

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We propose a model describing the interaction of an electron confined in a spherical box with a polar molecule in the center of the box, including an inner repulsive potential. As a preparation to its investigation, we calculate the average radius of a dipole-bound nonconfined electron, for which a closed form expression is found. The angular dependence of the wave function is also discussed, with implications for the choice of basis functions for ab initio calculations. The Schr"odinger equation in the spherical box is then solved. The negative energy eigenstates of the system and the dependence of the ground-state energy on the radius of the confining sphere are obtained. Interestingly, a very simple expression is found for the total number of negative energy levels for a given dipole strength and confining sphere radius.
Abstract We consider the quantum problem of a particle in either a spherical box or a finite spherical well confined by a circular cone with an apex angle 2θ 0 emanating from the center of the sphere, with 0 < θ 0 < π. This non-central potential can be solved by an extension of techniques used in spherically-symmetric problems. The angular parts of the eigenstates depend on azimuthal angle φ and polar angle θ as P λ m ( cos θ ) e im φ where P λ m is the associated Legendre function of integer order m and (usually noninteger) degree λ. There is an infinite discrete set of values λ = λ i m (i = 0, 1, 3, ...) that depend on m and θ 0. Each λ i m has an infinite sequence of eigenenergies E n ( λ i m ) , with corresponding radial parts of eigenfunctions. In a spherical box the discrete energy spectrum is determined by the zeros of the spherical Bessel functions. For several θ 0 we demonstrate the validity of Weyl’s continuous estimate  W for the exact number of states  up to energy E, and evaluate the fluctuations of  around  W . We examine the behavior of bound states in a well of finite depth U 0, and find the critical value U c (θ 0) when all bound states disappear. The radial part of the zero energy eigenstate outside the well is 1/r λ+1, which is not square-integrable for λ ≤ 1/2. (0 < λ ≤ 1/2) can appear for θ
The problem of two Coulombically interacting electrons confined in a cylindrical potential box with impenetrable walls is solved by the method of full configuration interaction (CI) for states with zero axial component of the total orbital angular momentum, including the ground state ${}^{1}{\ensuremath{\Sigma}}_{g}^{+}$. The number of variables in the Schr\"odinger equation is reduced from six to five by separating the ${\mathrm{L\ifmmode \hat{}\else \^{}\fi{}}}_{z}$ operator from the complete Hamiltonian. Two-electron basis sets of symmetry-adapted configuration state functions are constructed from real eigenfunctions of the one-electron Hamiltonian for a cylindrical potential box. Kinetic energy integrals are evaluated analytically. Electron repulsion integrals are computed by developing a separable expression for the 1/r121/{r}_{12}1/r12​ operator in the form of a double Fourier-Bessel-Fourier-cosine series and using enough terms to achieve a relative accuracy of ${10}^{\ensuremath{-}10}$ for the eigenvalues. Energy-level ordering and electron densities of selected electronic states are reported for cylindrical cavities of varying size with a fixed 1:1 length-to-diameter ratio. A remarkable feature of this system is that convergence of the full CI energy with respect to the one-electron basis set varies dramatically with the extent of confinement: For small cavities, the rate of approaching the basis-set limit is similar to that for two-electron atoms but is significantly faster for large cavities. Formation of singlet and triplet Wigner molecules is observed in cylindrical cavities with radii greater than about 5 bohrs.
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We study the problem of N electrons confined to a hard three-dimensional spherical box, for N = 3,4 and 5. Full-configuration interaction and Hartree–Fock calculations have been performed. We report energies, densities, second-order density matrices and exchange–correlation holes. In the N = 4 system, we observe a spin transition as the radius R of the sphere is increased, changing the ground state from 3 P to 5 S. The N = 3 and 5 systems remain 2 P and 4 S, respectively, for all R investigated. Pair-correlation functions and physical exchange–correlation holes have been computed over a regime in which the systems transform from liquid droplets to Wigner molecules. These functions show marked, yet characteristic, changes in this regime. By computing | E c / E |, where E c is the correlation energy defined with respect to the unrestricted Hartree–Fock solution, we show that the maximum relative error in the UHF energies occurs in this crossover regime. These systems provide challenging benchmarks for post-Hartree–Fock and density functional theory methods.
We study a system of two electrons interacting with a Coulomb potential in a sphere of radius R, bounded by an infinite wall using exact diagonalization. We have also investigated the influence of an additional parabolic potential (of strength k)k)k) arising from a uniform background smeared throughout the sphere. The convergence of the ground state energy of the singlet spin state of the system is investigated as a function of sphere size (essentially rs,{r}_{s},rs​, the Wigner--Seitz density parameter) for cases where there is no background potential (k=0)(k=0)(k=0) and for when $k\ensuremath{\ne}0.$ With k=0k=0k=0 and small rs,{r}_{s},rs​, we observe a maximum in the ground state density at the origin of the sphere. At ${r}_{s}\ensuremath{\approx}8\mathrm{a}.\mathrm{u}.,$ the ground state density acquires a minimum at the origin. For this and larger systems we identify the formation of a ``Wigner'' molecule state. We further investigate the ground state density as a function of k and also the correlation hole density as a function of rs{r}_{s}rs​ and k. We invert the Kohn--Sham equation for a two electron system and calculate the local effective potential and correlation potential (to within an additive constant) as functions of the radial coordinate for a number of values of rs{r}_{s}rs​ and k.
We consider a Dirac particle in a spherical box with a time-dependent radius. Analytical and numerical solutions of the time-dependent Dirac equation with time-dependent boundary (Dirichlet) conditions are obtained. Using the obtained solutions, physically observable characteristics of the dynamical confinement, such as the average kinetic energy (as a function of time) and average quantum force acting on the particle by the moving wall, are calculated. The trembling motion is analysed by computing the average coordinate of the Dirac particle as a function of time. The absence of the geometric phase is shown by direct calculation.