Geometric Model: Chemistry Notes

By Jack R. Woodyard

Abstract: Foundations of chemistry—The geometric model for multiple atoms is derived from first
principles. Preliminary thoughts.

Introduction
Definition of Terms
Atom is a synonym for a manifold.

Bond is any link-up between atoms.

A dyad is any two electrons/modules taken together in an interaction.

Effective nuclear charge, β , is necessary for the (atomic) Virial Theorem.

Electron is a synonym for a module.

A graphical representation is a visible geometric figure.

An ion is an atom with either a surplus or deficit of electrons.

A mathematical representation is the set of equations and parameters necessary to calculate a graphical representation.

A manifold is the combination of modules to form a graphic representation.

1. Symmetry is important for atoms, but less so for molecules.

2. Atomic modules must be as far apart as possible, while as close to the nucleus as possible.
3. Molecular modules consist of atomic manifolds placed by reference to the valence electrons.

A m-manifold is constructed in the manner of the atomic manifolds, but with atomic manifolds as modules.

Module:

1. One nucleus—the interaction between an electron and a nucleus. It is made of Schrödinger functions.
2. Multi-nuclei—the interaction between manifolds representing the atoms/ions in a molecule, etc.

Molecule—a combination of two, or more, atom manifolds used as modules used in constructing a m-manifold. As used
in this model it also represents glasses, liquids, gasses, etc.

Paired electrons are any two electrons/modules having the same, non-spin, quantum numbers. Spins are opposed.

Schrödinger functions are any solutions to the one-electron, Schrödinger, time-independent equation.

Separation parameter,

1. One nucleus—ε⃗ , is the distance between the center of mass of a module and the origin of the manifold.
2. Multi-nuclei—δ⃗ , is the distance between nuclei.

Spacetime is a four-dimensional representation of the volume containing the manifold.

Valence electrons form dyads between separate atoms, or vacate the atom to form ions.

The Virial Theorem is a proven mathematical relationship pertaining to bound systems.

Principles
1. In chemical reactions, atoms/ions retain their integrity.
2. All bonds are binary, i.e., the total bond energy is the sum of binary interactions.
3. Only the valence electrons are used in any calculations.
a. Covalent bonds require at least one unpaired electron in each atom.
i. Unpaired electrons from one atom work with unpaired electrons from another atom for the
simplest form.
ii. Weakly bonded paired electrons in one atom may be used in bonds with another if the energy is
right, but the bonding/antibonding relation must be retained.
b. Ionic bonds require ions with no unpaired electrons.
c. Metallic bonds require an ion core with a sea of somewhat free valence electrons.
i. The degree of conductivity is determined by the degree of freedom of the valence electrons.
ii. Metallic bonds are a bulk effect.
d. Van der Waals bonds require neutral molecules with no unpaired electrons.
4. Any bonded system may have both covalent and ionic forms. Each form is calculated separately, and the
tendency of one atom to give up electron(s) to another measures the degree of covalency.
5. A full system may require any or all forms of bonds.
6. Glass, alloys, accretions, liquids, and gasses may be modeled.

When developing this model for atomic systems, it was discovered that three equations were required: Schrödinger’s
time-independent equation, Schrödinger’s time-dependent equation, and The Virial Theorem. As the separation
parameter, ε ( t ), is quantized, so must time be quantized. Indeed, the very use of the time dependent equation for a steady
state situation requires it.

Molecules are considerably simpler. The presence of nuclei, and the ability of the atom to retain its identity, precludes the
formidable interaction with quantum foam. Thus, the time-independent equation, and the Virial Theorem are all that are
required to model the system. The Virial Theorem provides the δ⃗ factors for each dyad of the valence modules.

Manifold
In the atomic case, the modules take the form: ψ i ( β , ⃗ε , ⃗r ) referenced to the manifold origin centered on the nucleus. The
N
1
total wavefunction, i.e., manifold, has the equation: Ψ ( β , ⃗ε , r⃗ )= ∑ ± ψ ( β , ⃗ε , ⃗r ).
√ γ i=1 i
The +¿ is required for paired electrons. The ± is chosen by the sum of the spins of the dyads used for square-magnitude
manifolds. Using angular momentum, i.e., LS- or JJ-coupling, the signs of the module along with the magnetic quantum
numbers are chosen to give the proper angular values.
space
1
The normalization coefficient is γ , found from the square magnitude of the manifold. This takes the form: 1=
γ
∫ 2
Ψ dτ
all
, Thus
N N space
γ ( β , ⃗ε )=∑ ∑ ∫ ψ i ψ j dτ
i=1 j=1 all
When two, or more, atoms are used as modules, m-modules, in a molecular manifold, m-manifold, each m-module may
1
have its own β and ε values. Thus, in a diatomic molecular system, Ψ m = ( Ψ a 1 ( β a1 , ε a 1 , ⃗r ) +Ψ a 2 ( β a 2 , ε a 2 , r⃗ ) ). The
√ γm
mean values of operators will require the atomic parameters for both m-modules. 1

Even more than in the atomic case, the paired electrons become spin-zero, mass-two bosons. There is a caveat. In some
instances, the spin-spin relationship is stronger than the ionization potential. For beryllium, the valence electrons are
paired. Thus ionization removes both, simultaneously. For some multi-valence systems, a similar thing may happen. This
might possibly be described as requiring an excited state of the multi-valence system before bonding may occur.

1
This is equally true for calculating transition probabilities for atomic, excited states.
 Chemistry
Chemistry is a macroscopic science, underpinned with quantum mechanical concepts. Chemists worry about Avogadro’s
number; moles of reactant, moles of product, moles of catalyst, etc. This is important when comparing calculated values
with experiment. You have to determine the conditions, and method of manufacture, the temperature and pressure of the
product, and so on. Bond strengths, bonding angles, bond lengths … are important too.

Chemists study: Covalent bonds, ionic bonds, metallic bonds, and van der Waals bonds; and combinations there-of. To
compare to the literature, one must calculate the enthalpy, H=E + pV , for the actual bonded modules.

Covalent Bonds
Pure covalent bonds require absence of local ions. At least two valence modules must be involved, pairwise.

Kinetic Energy
The Laplacian term is as before, but applied to each a-module in turn. Stabilization by multiple nuclei negates quantum
scattering. The system becomes effectively macroscopic.

Potential Energy
Each nucleus will have its own electrostatic potential. Such will not only impact its modules, but those of all the other
nuclei, as well. The total potential energy will be the sum of all of these.

Virial Theorem
With the atomic-modules pre-determined the Virial theorem is relegated to finding the bond lengths, etc.

Examples
Modules/atoms are laid out according to the manifold being calculated. As with the atomic models, the manifold must be
chosen for each model.

Diatomic Hydrogen
Manifold
This is very much like the model for the negative hydrogen ion. With two nuclei, one
may place the origin as desired. Choose the center-of-mass of the system. The half-
separation should be δ . The ε in the manifold is for the negative hydrogen ion.

Modules

ψ 1 (1 , δ , r⃗ ) =
π√
13 −1 √ r +δ −2 rδcos θ
e
2 2

ψ 2 (1 , δ , r⃗ )=
√ 13 −1 √ r +δ +2 rδ cos θ
π
e
2 2

1
Ψ ( 1 , δ , ⃗r )= [ ψ 1 ( 1 , δ , ⃗r ) +ψ 2 (1 , δ , r⃗ ) ]
√γ
Normalization
 [ ] [ ]
space space
γ =2 ZN 1+ 2 ∫ ψ 1 ψ 2 dτ = 4 1+2 ∫ ψ 1 ψ 2 dτ
all all

as there are two nuclei as well as two electrons/modules.

Time-Independent Equation
Kinetic Energy

{∫ [( ∫ √ )]}
space 2 space space
2 ψ1 ψ1ψ2
T n= 4 dτ −1+ 4 dτ− ∫ ψ 1 ψ 2 dτ
γ all √r 2 +δ 2−2 rδ cos θ all
2
r + δ −2 rδ cos θ
2
all

Potential Energy
Counting both nuclei:
space 2
−4 ( ψ 1+ψ 2)
V n=
γ
∫ r
dτ
all

Covalent Lithium Hydride

Lithium hydride is believed to have both covalent and ionic instances.

1
Ψ ( δ , r⃗ )= [ ψ Li ( β , δ , r⃗ )+ψ H (1 , δ , r⃗ ) ]
√ γa

Ψ ( δ , r⃗ )=
1
√ γa [ 1
√ γ Li
[ ψ 2 s ( β Li , 0 , ⃗r ) +ψ 1 sa ( β Li , ε , ⃗r ) +ψ 1 sb ( β Li ,−ε , ⃗r ) ] +ψ H ( 1 , δ , ⃗r ) ]
√
ψ 1 sa ( β Li , ε , ⃗r )=
β Li3 −β √r +ε −2rε cos θ
π
e Li
2 2

ψ 1 sb ( β Li ,−ε , ⃗r )=
√ β Li3 − β √r +ε +2 rε cos θ
π
e Li
2 2

√ β Li3
( β Li r −β2
)
Li r

ψ 2 s ( β Li , δ , r⃗ ) = 1− e
8π 2
 √ 1 −1 √ r + δ −2 rδsin θ cos θ cos ϕ
2 2

ψ Li (1 , δ , r⃗ ) = e
π

There are cases where materials exist with either covalent or ionic bonding or some combination of the two. This may be
studied by calculating both conditions, and noting any preference for one module over another in the covalent system.

Bond angles are demonstrated in the valence modules of the base atomic manifolds.

Ionic Bonds
Pure ionic bonds require local ions that produce all of the interaction.
−¿¿
Ionic-bonded lithium hydride requires an Li +¿− H ¿ ion combination. It will have an appropriate time-independent
equation, and the bond length will be determined by the Virial Theorem.

Bond angles are demonstrated in the valence modules of the base atomic manifolds.

Metallic Bonds
Metallic-bonded hydrogen will have properties of both ionic and covalent bonding. The cores will act like ions in a
“plumb pudding.” The valence electrons will produce a “lumpy soup.” The time-independent equation will produce the
energy, while the Virial Theorem will produce bond lengths.

Bond angles are demonstrated in the valence modules of the base atomic manifolds.

Van der Waals Bonds

Van der Waals bonded solid helium has atomic manifolds sufficiently “sticky.”

Again, the time-independent equation will produce the energy, while the Virial Theorem will produce bond lengths.

Bond angles are demonstrated in the valence modules of the base atomic manifolds.

Further Work
A series of tests, found in Appendix 7: Gradient Model, were designed:

1. Elucidate the form and function of the four types of bonding.

2. Determine if the model would give results adequate to pursue.2

It was determined that the bond length could be adequately determined by;

1. Making the separation, δ , the hypotenuse of a triangle made from the ε -vaues of the two interacting modules
for covalent bonds.
2. Making δ the vector sum of the interacting modules of the valence dyad for ionic bonds.
3. Building N × N × N cubes of metallic atoms to study edge, side, and bulk issues for metallic bonds.
4. Arrange patterns of neutral manifolds so that the origination of the structure disappears to study van der Waals
bonds.

As these notions came directly from the Schrödinger function models. They should be readily proven mathematically.

We summarize:

Diatomic Hydrogen (covalent)

Experimental Bond Dissociation Energy: 0.1661
2
Yes.
 Experimental Bond Length: 1.4003

Calculated Bond Dissociation Energy: 0.1711

Calculated Bond Length: 1.4142

Lithium Hydride (ionic)

With this system there are two super-modules: Li+ and H- . For Li+ ε Li =0.1462353 ; Z Li=3

For H- ε H =0.9361809 ; Z H =1

The in-line distance between centers of action is3 ζ =ε Li + ε H =1.08242 .

Lattice constant = 9.185

Experimental = 9.1351

Ionic crystals have an interesting structure. Because there are no cross-terms between the super-modules, the energy of the
system is the sum of the energies of the ions. For the negative hydrogen ion E = -0.5377, and for Li II E = -7.3685, for a
total energy of the molecule, E = -7.9062. To find the energy stored in the crystal, simply subtract the sum of the energies
of the neutral atoms. Hydrogen has E = -0.5; lithium has E =- 7.2764 so stored energy = 0.1298. The accepted value for
enthalpy of formation is -0.03453. To compare these, we must look at the process of formation.

If we take the stored energy per electron, we have 0.032. this compares to the enthalpy of formation at 0.03453 to be 92.7
per cent.

Metallic Hydrogen
A set of 1s electrons are strung together, i.e., assuming mono-atomic modules. The separation distance is 0.03. The
manifold is based on the mean radius of the hydrogen atom, 1.52. The modules all blend together into one large module to
make the manifold.

The modules add together, so they are basically alternating spins.

With the high pressure necessary I propose ε =0.015

The stored energy would be near E Li II =−7.3685

Van der Waals

Solid Helium
ε He =0.28107

E He =2.9735

The module centers of action are equidistant, so one can not determine which are interacting in the manner of bosons.

There is no unbalanced charge, so the bonding must be van der Waals. The trick is to model this geometrically as we have
the other bond types.

The listed heat of fusion is 3.35 X 10-5. To get this value we would need ε He =0.28114 . Compare to the calculated value,
0.28107, listed above.
3
√ 2 2
Actually, from the diagram, ζ = ε Li +ε H =1.0403 . The above estimate is off enough that the non-in-line is better.
 Comments
Outrageously “outside the box,” yet the geometric model produces great results:

1. Energy levels, bond lengths, and bond angles give values orders-of-magnitude better than traditional means.
2. Computational difficulty is vastly reduced.
3. Wavefunctions/manifolds can be used for:
a. Accurate calculation of such quantities as atomic transition probabilities, i.e., Einstein-A coefficients.
b. Accurate calculation for atomic and molecular visualization.
4. May well be extendable to other disciplines and materials.

Conjecture
1. Column II elements ionize with both of the valence electrons leaving at the same time. These valence electrons
are actually paired. Is it possible that they are a form of a Couper pair? Evidently, the binding of the Couper pair
is stronger than the ionization potential. Could one partially ionize the bulk metal and produce Couper pairs that
could then cause superconductivity? Lattice vibrations would likely confound such, but there may be a narrow
temperature window for such an effect. Likely the effect may increase with the activity of the subject metal.
Perhaps some form of precise, dilute, photon bombardment could produce the desired ionization pattern.
2. In atomic systems, paired electrons become spin-zero bosons because of the geometry of the system. Because
each atom, or excited state has its own β , and ε parameters these electrons must be included in the calculation
of bonding parameters, and in transition probabilities, i.e., Einstein “A” coefficients. If this effect is small enough
in the non-valence electrons, it would explain the remarkable success of the Gradient Model.