Electrostatics of Point Charges

(Electrons)

and atomic structure.

Tim P. LaFave Jr. | University of Texas at Dallas

2011
Why Focus on Electrons?

In Nature, the two most common charged particles are protons and electrons.
Electronic devices are primarily characterized by electrons as they are the most mobile
of the two.
Chemistry is predominantly based on electron interactions in atoms. Valence
(outermost) electrons tend to be the most loosely-bound.
Electrons are very small (femtometers, 10-15 m) compared to the dimensions
(nanometers, 10-9 m) over which we are interested here, so we may approximate them
as mathematical points of charge.
Electrostatics is concerned only with charges that do not move.
Here we will only consider electrons. However, most of what is discussed here may
apply to other charged particles.
 How much energy is stored in a system of two electrons?

To answer this, we conventionally use a method of charge assembly

A. Assume that we know the location of each electron in the system (r1 and r2).
B. Remove both electrons (e1 and e2) to infinity (so they no longer interact)
C. Evaluate the work done to re-assemble the charges to their original locations.

e2 e2 e1 e1

r2 r1

e2 e2 e1 e1

r2 r1
 Evaluation of work done to re-assemble the system
The work done to move the first electron, e1, to r1 is zero since there is no electric field
to fight against.
e2 e2 e e1
1

r2 r1

The work done to move e2 to r2 is evaluated by the electrostatic force applied by you
against the electric field due to e1.
e2 F = e2E e2 e e1
1

r2 r1

Given, (eq. 3.3, Slater)

How can two electrons form a stationary system in free space?
In Nature, e1 will be repelled by e2 as it arrives from infinity.
Q: How much force is needed to hold e1 in place?
A: F = -e1E acts on e1, so F = +e1E is needed to hold it in place.
Associated with this force is an energy

(which equals the work you did on e2)

Q: Why isnt the total energy stored equal to twice the work done to assemble it?
A: Suppose something holds e1 in place (imagine anchoring it to a spring). The arrival
of e2 results in the displacement of e1. So when you act on e2 you must supply energy
to cause this displacement (a response) AND the energy needed to place e2 in
position. Initially, all the energy goes into displacing e1, but when you let go of e2
(provided it is also anchored with a spring), its interaction with the electric field due
to e1 causes e2 to also be displaced with an equal, but opposite force acting on e2.
Hence, the two displacements are the result of mutually-distributed energy stored in
the system. e e
2 1

W
e2 e1

W/2 W/2
Alternative evaluation of stored energy

We could have simply added up both electrostatic interaction terms

W = e1V(e2) + e2V(e1)
and argued that only e2V(e1) supplies energy to the system, so e1V(e2) = 0, but this
doesnt reveal the underlying mechanics or physics very well.
Instead, if we write,

we explicitly take both interactions into account that is, the work needed to assemble
the system is equally divided between the response of e1 to V(e2) and the response of
e2 to V(e1).

Note: Coulombs Law implicitly takes this mutual distribution of energy into account.
Evaluation of stored energy in N-electron system

To the 2-electron system, you must do work on e3 associated with the electrostatic
forces acting on e3 by the electric fields of e1 and e2, that is,
W = e3V(e1) + e3V(e2)
such that the total stored energy is
U(3) = U(2) +W
which may be fully written

Or for N electrons: or (p.95, eq. 3.2 Slater)

We could have written this in an explicit interactions framework as before,

and immediately recognize that the factor of appearing in the boxed equation above
is necessarily the result of mutual electrostatic interactions of every pair of electrons.
This is implied by Slaters eq. (common among textbooks), but not very clear.
Charge assembly in any sequence gives the same result

It does not matter in which order you assemble electrons to the system. In fact, you
could assemble them all at the same time (simultaneously), if you knew their final
locations, and still get the same result.
Consider charge assembly again,
A. Know locations of all electrons.
B. Disassemble to .
C. Re-assemble all electrons simultaneously.
As charges approach from , they cannot all approach in one bundle (e.g. already
assembled), so they must all be as far apart as they can possibly be.
Since they will all arrive simultaneously they must each be at the same distance from
the system at any moment in the assembly process.
Thus, the charges form an imaginary surface of a sphere as they are assembled.
This configuration of electrons (or any charges of equal magnitude and sign) is known
at the THOMSON PROBLEM.
The Thomson Problem

Objective: Determine the minimum energy configuration of equal charges (electrons)

distributed on a unit sphere. (unit sphere indicates that the size of the sphere is
irrelevant.)

For 2-electrons, the electrostatic (minimum energy configuration) solution of Thomsons

problem is obtained when electrons are on opposite sides of the origin.

For 3-electrons, electrons are at the vertices of an equilateral triangle.

For 4-electrons, electrons are at the vertices of a regular tetrahedron.

For 5-electrons, two electrons reside at the north and south poles of the sphere, and the
remaining three form an equilateral triangle about the equator.
The Thomson Problem and the Plum Pudding model of the atom

Recall: J.J. Thomsons Plum-Pudding model of the atom consists of electrons confined
to a spherical positive volume charge.

If we strip away the positive volume charge, the electrons repel in such a way that they
eventually take up positions at the same distance from the origin and form solutions of
the Thomson Problem.

So the Thomson Problem is a natural result of the plum pudding model without the
positive volume charge.

J.J. Thomons Classical model of the atom (1904)

The Thomson Problem and Atomic Structure

I found an intriguing pattern, a fingerprint, that is consistent with changes in atomic

structure as you add or remove an electron.
Consider how to change the spatial symmetry of each system without losing any charge.
If we move one electron from the 5-electron configuration, and allow the remaining two
to relax on the sphere they form the 4-electron solution of Thomsons problem. Hence,
the total charge doesnt change, but the symmetry changes from 5- to 4-electron
symmetry.

The energy needed to make this transition is U.

Energy due to discrete symmetry changes

In a plot of U, the energy distribution has non-uniform jumps that coincide with
changes between electron orbital (wavefunction) geometries. For example, a jump
appears between the 2s and 2p shell between N=4 and N=5.
Energy due to discrete symmetry changes in QUANTUM DOTS

If we model spherical quantum dots as simple dielectric spheres containing discrete

electrons, we may consider solutions of the Thomson problem within the dielectric
sphere and vary the Thomson radius within the sphere until a minimum energy is
obtained.

The respective changes in symmetry lead to a very similar distribution of U.

Energy due to discrete symmetry changes in QUANTUM DOTS

The distribution of U when the Thomson problem is treated inside a dielectric sphere
yields much more pronounced jumps between energies than the Thomson Problem
treated on a unit sphere in free space.
Compared with empirical data

You may have noticed four LARGE dips in energy. These coincide with large dips in
EMPIRICAL (measured) data of size-independent ionization energy of the atoms.

Size-Independent ionization energy:

(Ionization energy) (atomic radius)
A periodic pattern

If we consider only the largest dips in energy, and plot U for Thomsons Problem in free
space up to N=500, we find a regular, periodic occurrence for up to about 100 electrons.
This regularity is NOT found for N>100! (Is this related to the Periodic Law?)
What might be the underlying mechanism of the Periodic Law?

Conjecture:
Discrete charges constrained to three dimensional spherical region of space (e.g. inside
a dielectric sphere or in the central potential well of an atomic nucleus) are restricted
to varying degrees and properties of spatial symmetry. This yields the wide variety of
physical and chemical properties of the elements.
Symmetry restrictions

Example: 1s and 2s orbitals are both spherically symmetric, but the 2p orbital is
a dumbbell shape (Z=5). Why not spherical? Why do we see an abrupt jump in
the energy?

Note that N=1,2,3,4 are all highly symmetry configurations.

N=1 and N=2 are rather trivial, but exceptionally symmetric (spherical and
cylindrical)
For N=3 and N=4, all electrons in each are equidistant from all other electrons
(equilateral triangle and regular tetrahedron).

For N=5, however, this global equidistance symmetry property is not possible in
three-dimensional space. Thus, this restriction impacts the lowest possible energy
of the 5-electron system, and results in a change in the orbital symmetry.

Something to try: A similar example is to try drawing four points on a flat sheet of
paper such that all points are equidistant from all others. You may convince
yourself that this is also impossible.
Concluding Remarks
J.J. Thomson may have been on the right track, but likely never thought of the problem
in this way. There is much more work to be done.
Why pursue this?
Quantum mechanics gives results by mathematics, but quantum theory provides us no
further insight or explanation of how it all works. Schrodingers equation is designed for
the kinetic (dynamic) properties of particles in a system. The classical Poissons equation
(and Laplaces equation) are designed for the potential (static) properties which are
typically used as variational parameters in Schrodingers equation to converge upon the
ground state energy of a system, for example. However, this approach yields the absolute
lowest possible energy state of the system (in the absence of all kinetic energy).

Engineering and Device Design Considerations

Instead of simply resorting to quantum mechanics for modeling nanoscale devices
containing few discrete electrons, consider how the classical electrostatics of the system
may improve our understanding of the electronic properties and allow us to design and
fabricate better devices.
Related References
1. T. LaFave Jr, Discrete transformations in the Thomson Problem, J. Electrostatics
72(1) 39-43 (2014).
2. T. LaFave Jr, Correspondences between the classical electrostatic Thomson Problem
and atomic electronic structure, J. Electrostatics 71(6) 1029-1035 (2013).
3. T. LaFave Jr, Discrete charge dielectric model of electrostatic energy, J. Electrostatics
69(5) 414-418 (2011).
4. T. LaFave Jr and R. Tsu, The value of monophasic capacitance of few-electron
systems Microelectron. J. 40(4-5) 791-795 (2009).
5. T. LaFave Jr and R. Tsu, Capacitance: A property of nanoscale materials based on
spatial symmetry of discrete electrons, Microelectron. J. 39(3-4) 617-623 (2008).
6. J. Zhu, T. LaFave Jr and R. Tsu, "Capacitance of few electron dielectric spheres,"
Microelectron. J. 37(11) 1293-1296 (2006).
7. R. Tsu & T. LaFave Jr, Role of symmetry in conductance, capacitance, and doping of
quantum dots in The Wonder of Nanotechnology: Quantum Optoelectronic Devices
and Applications M. Razeghi, L. Esaki, and K. von Klitzing, Eds., SPIE Press, pp. 3-38
(2013).
8. 2014 Correspondences Between The Classical Thomson Problem and The Periodic
Table of The Elements http://www.tjlafave.com/DCD/Pubs/LaFave-Thomson-
Problem-Poster-3.pdf