Sustained Oscillating Collisions Between Two Monoatomic Molecules

Vol.
6, 2021-14
Sustained Oscillating Collisions between Two Monoatomic Molecules
Hugo Hernandez
ForsChem Research, 050030 Medellin, Colombia
hugo.hernandez@forschem.org
doi: 10.13140/RG.2.2.29666.86724
Abstract
Sustained oscillating collisions between two monoatomic molecules can only begin or end
under very specific conditions, involving external forces or multiple-body interactions. The
dynamic equations describing such sustained oscillation are presented. These expressions can
only be analytically solved for relatively simple intermolecular potential functions, like for
example, the quadratic or harmonic potential, and the cubic potential. These two models can
also be used as approximations of more complex nonlinear interaction potential functions.
Considering the Lennard-Jones potential function as an example, it is shown that the cubic
approximation provides a wider range of validity than the classical harmonic approximation.
However, due to the lack of analytical solutions for other functions and approximations,
numerical simulation remains the key tool for describing oscillating collisions.
Keywords
Collision Dynamics, Cubic Approximation, Equations of Motion, Harmonic Potential,

Intermolecular Potential, Lennard-Jones, Molecular Interaction, Oscillation.
1. Introduction
In a previous report [1], the dynamic behavior during the collision of two monoatomic
molecules was analyzed. In this report, a particular situation will be explained and discussed,
corresponding to the sustained oscillating collision between the molecules.
Most collisions between two bodies, in the absence of additional bodies and external forces,
occur only once. This is due, first of all, because a collision can only occur when the two bodies
are initially approaching each other. If they enter by inertial motion into their corresponding
spheres of action [2], then after the collision, they begin separating from each other and will
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Sustained Oscillating Collisions between
Two Monoatomic Molecules
Hugo Hernandez
ForsChem Research
not collide again, unless external forces or interactions with other bodies alter their resulting
inertial motion.
Two conditions are required for a sustained oscillating collision between the same pair of
molecules, in the absence of external forces or interactions: 1) Their relative molecular velocity
must be zero when the intermolecular interaction potential is significantly attractive (that is,
they do not enter into their spheres of action by inertial motion), and 2) the collision is aligned.
Multiple unaligned collisions are not possible in the absence of external forces or interactions.
Of course, the first condition always necessarily guarantees the second condition in the
absence of external forces or interactions.
However, the previously mentioned first condition cannot be met in the absence of external
forces or interactions. Thus, for our present analysis, we will assume that such external force or
interaction is no longer present as soon as the first condition (and therefore also the second
condition) is met. Similarly, an external force or interaction is needed to stop the sustained
oscillating collision between the molecules. The emergence and the end of oscillating collisions
is basically the result of multiple-body interactions, which is beyond the scope of the present
analysis.
The dynamic equations describing sustained oscillating collisions between two monoatomic
molecules are presented in Section 2. These equations can be solved analytically for relatively
simple intermolecular potential functions. The results obtained for the most important
approximations (quadratic and cubic approximations) to the interaction potential functions are
illustrated in Section 3. Finally, a common model of intermolecular potential (the Lennard-Jones
potential function) is considered and discussed in Section 4.
2. Dynamics of Sustained Oscillating Collisions
The system considered is presented in Figure 1. We will assume that the -axis is aligned with
the center of mass of the molecules. The relative molecular velocities of the molecules are zero
for all the positions depicted. The last state exactly corresponds to the system initial state.
The equations of motion for this system are identical to those of any other collision [1]:
( )
(2.1)
( )
(2.2)

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Figure 1. Schematic representation of the oscillating collision between two monoatomic

molecules. Horizontal axis ( ): Position along the line connecting their centers of mass. Vertical
axis ( ): Time. : Molecular mass. ⃗ : Intermolecular force (dashed-dotted arrows). Dashed
green line: Intermolecular distance. Subscripts and and colors (blue and orange) represent
different molecules.
These equations can be expressed in terms of the relative molecular velocity and relative
molecular position as follows:
( )
(2.3)
The main difference of sustained oscillating collisions with respect to any other collision is the
particular set of initial conditions (considered at the beginning of each oscillation):
( )
(2.4)
( )
(2.5)
For these conditions, the solution (integration) of the simplified equation of motion (2.3) is:
( ) ( )∫
(2.6)
( ) ( ) ( )∫ ∫
(2.7)

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Eq .(2.3) can also be alternatively expressed as follows:
( )
(2.8)
which results in the following total energy conservation equation:
( )
( ) ( ) ( )
(2.9)
From these expressions we can conclude that the dynamic behavior of the relative molecular
velocity and position necessarily depends on the interaction potential between the molecules.
It is also possible to conclude that at the moment of collision (when the minimum
intermolecular distance is achieved), the interaction potential becomes:
( ) ( )
(2.10)
since the relative velocity at time for aligned collisions is also zero (see Figure 1).
With these relations in mind, let us consider different types of intermolecular potential
functions.
3. Approximated Intermolecular Potentials
Before considering any specific intermolecular potential function, let us notice that those
functions are constrained by the following conditions:
 The intermolecular potential must be the same at both the minimum ( ) and
maximum ( ) intermolecular distances.
 The maximum intermolecular potential value ( ) is obtained at the extreme
intermolecular distances (where the kinetic energy is zero).
 There is a minimum intermolecular potential value ( ) located at an arbitrary
intermolecular distance such that .
These conditions can be mathematically expressed by the following set of equations:
( ) ( )
(3.1)

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(3.2)
(3.3)
( )
(3.4)
(3.5)
(3.6)
The intermolecular potential function must be necessarily nonlinear, or otherwise, the

conditions given in Eq. (3.2), (3.3) and (3.6) cannot be fulfilled. Let us now consider some
relevant nonlinear approximations describing intermolecular potentials.
3.1. Quadratic (Harmonic) Potential
The simplest approximation to any nonlinear function is the quadratic model. It can be
considered as an infinite series (i.e. Taylor series) approximation truncated after the second
order term. The quadratic or parabolic potential model can be generally expressed as follows:
( )
(3.7)
Then, conditions (3.1) to (3.6) become:
(3.8)
(3.9)
(3.10)
(3.11)

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(3.12)
(3.13)
Solving this set of equations we obtain:
( )
( )
(3.14)
(3.15)
This solution is the only possible quadratic model fulfilling the required conditions. Notice that
we have 4 parameters ( , , and ) and only 4 equalities among the conditions.
Therefore, for the quadratic potential, Eq. (2.3) becomes:
( ) ( )
( )
(3.16)
Now, using the following transformations:
(3.17)
√ ( )
( )
(3.18)
Eq. (3.16) can be expressed as:
(3.19)
which is the classical expression of a linear simple harmonic oscillator with the following
dynamic behavior [3]:
( ) ( )
(3.20)
where

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(3.21)
(3.22)
and , corresponding to the frequency of oscillation, is given by Eq. (3.18). Thus, Eq. (3.20)
becomes:
( ) ( ) ( ) √ ( ) ( )
( )
( )
(3.23)
and with the following dynamic expression for the relative molecular velocity:
( ) ( )√ ( )
( )
√ ( ) ( )
( )
( )
(3.24)
Furthermore, the dynamic behavior of the intermolecular potential is given by:
( ) ( ) √ ( ) ( )
( )
( )
(3.25)
The dynamic and spatial behavior of these variables for the quadratic potential approximation
is graphically summarized in Figure 2 and Figure 3, respectively. Notice that the loop obtained
by plotting the relative velocity with respect to the relative position is always taking place in
the clockwise direction.

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Figure 2. Dynamic behavior of oscillating collisions for a quadratic intermolecular potential

approximation. Blue line: Dimensionless relative position. Red line: Dimensionless relative
velocity. Green line: Dimensionless intermolecular potential.
Figure 3. Spatial behavior of oscillating collisions for a quadratic intermolecular potential

approximation. Red line: Dimensionless relative velocity. Green line: Dimensionless
intermolecular potential.

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Hugo Hernandez
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3.2. Cubic Potential
If the depth of the potential well ( ) is large, the nonlinear behavior of the
intermolecular potential might not be well approximated by a quadratic function. By
considering an additional term in the series approximation, a cubic function is obtained. The
corresponding approximated potential function is:
( )
(3.26)
Since we have now four parameters in this function, and is also unknown, there are many
cubic functions satisfying the conditions for oscillating collision. However, if we do know the
value , then the conditions determine all the coefficients of the cubic model.
Assuming to be known, the cubic potential function satisfying all conditions is:
( ) ( ̂ )̂ ( ̂ )̂ ( ̂ )̂ ̂ ̂ (̂ )
̂ (̂ )
(3.27)
where
(3.28)
(3.29)
and ̂ is subject to the following constraint:
̂
(3.30)
Values of ̂ outside this range cannot be adequately described by the cubic approximation.
Using these expressions, Eq. (2.3) becomes for the cubic approximation:
( ̂ )̂ ( ̂ )̂ ( ̂ )̂
̂ ( )
( ) ̂ (̂ )
(3.31)
or equivalently,

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̂ ̂ ̂
(3.32)
where
( ̂ )
̂ (̂ )
(3.33)
( ̂ )
̂ (̂ )
(3.34)
( ̂ )
̂ (̂ )
(3.35)
and is given by Eq. (3.18), analogous to the harmonic potential case.
Since the analytical solution to the differential equation (3.32) is not straightforward (as in the
previous case), it can be solved numerically, or approximated using the following expression:
( ) ( ( ) ) ( ( ) )
( ̂ )( ) ( ̂ )
(3.36)
where
√ ( ̂ ) ( ̂ ) ( ̂ )
(3.37)
is the last time of maximum intermolecular distance, and is the time of the last collision,
which can also be expressed as follows:
( )
⌊ ⌋
(3.38)
( )
(⌊ ⌋ )
(3.39)
The results obtained by simulation (numerical solution of the ODE system) and by the
approximate solution (3.36), for different values of ̂ , are illustrated in Figure 4 to Figure 8.
Figure 6 ( ̂ ) is equivalent to the quadratic approximation described in the previous

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section. The only difference is the normalization of the relative molecular position, which is not
expressed in terms of ̂ in the cubic case. In addition, the cubic approximation clearly
provides more versatility than the simple linear harmonic approximation.
Figure 4. Dynamic (left plot) and spatial (right plot) behavior of oscillating collisions for a cubic
intermolecular potential approximation with ̂ . Blue line: Dimensionless relative
position (numerical simulation). Purple dashed line: Approximate dimensionless relative
position (Eq. 3.36). Red line: Dimensionless relative velocity. Green line: Dimensionless

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Additional approximations are possible by increasing the order of the polynomial. However,
the complexity of the solutions (both exact and approximate) also increases, being limited
almost exclusively to numerical integration (simulation). However, if numerical simulation is
used, the original intermolecular potential function without approximation can be directly
employed, as illustrated in the next Section.
4. Lennard-Jones Intermolecular Potential Function
The Lennard-Jones intermolecular potential [4] can be expressed mathematically as follows:
( ) [( ) ( ) ]
(4.1)
where and are model parameters, associated to the minimum intermolecular potential and
the minimum possible intermolecular distance in sustained oscillation, respectively.
In fact, the minimum intermolecular potential of the Lennard-Jones model is located at the
intermolecular distance :

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(4.2)
and has a value of:
(4.3)
Let us now assume that the maximum intermolecular potential experienced by two
monoatomic molecules under oscillating collisions is . Then, the maximum and
minimum intermolecular distances during the oscillating collisions will be:
√
( )
(4.4)
√
( )
(4.5)
The normalized intermolecular position at minimum potential then becomes (from Eq. 3.28):
[( √ ) ]( √ )
̂
( √ ) ( √ )
(4.6)
This expression is graphically represented in Figure 9, with the normalized intermolecular

position at minimum potential in the horizontal axis and a normalized intermolecular potential
range ( ) in the vertical axis. When ̂ , the cubic model is no longer adequate
for describing the potential function, because the position of minimum potential energy cannot
be correctly represented by the model. However, a cubic approximation could still be used but
with a reduced performance. Something similar occurs when the quadratic approximation is
used even though ̂ . The limiting potential values are preserved but the location of the
minimum potential energy changes. The goodness of the quadratic and cubic approximations
for different ranges of intermolecular potential limits is shown in Figure 10. Negative values
are omitted in the plot.

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Figure 9. Relationship between the normalized intermolecular potential range ( ) and

the normalized intermolecular distance at minimum potential ( ) for the Lennard-Jones
model. The dashed lines indicate the limit of adequacy of the cubic approximation.
Figure 10. Goodness of fit of the quadratic (orange line) and the cubic (green line)
approximations to the Lennard-Jones intermolecular potential as a function of the normalized
potential range ( ). The dashed line indicates an arbitrary limit of .
As expected, the quadratic approximation only provides a reasonable fit ( ) for

normalized potential ranges below , and it is never capable or adequately describing the
location of the minimum intermolecular potential. The cubic approximation, on the other hand,
correctly describes the location of the minimum intermolecular potential while providing a
goodness of fit larger than , for . For larger normalized potential
ranges, the goodness of the cubic fit decreases with a mismatch in the location of the minimum
intermolecular potential, reaching the limit when , and continues
dropping afterwards. Thus, for normalized potential range values larger than , numerical
simulation or a different approximation is best suited.

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As an example, Figure 11 to Figure 16 show the simulation results of the Lennard-Jones

potential model for different values of the normalized potential range. Figure 11 and Figure 12
can be approximately described by the cubic potential approximation. However, larger
potential differences require forcing different amplitudes for the oscillation, clearly deviating
from the real behavior of the system.
Figure 11. Dynamic (left plot) and spatial (right plot) behavior of oscillating collisions for a
Lennard-Jones intermolecular potential with . Blue line: Dimensionless relative
position (numerical simulation). Red line: Dimensionless relative velocity. Green line:
Dimensionless intermolecular potential. Purple dashed line: Cubic approximation.
Dimensionless intermolecular potential. Purple dashed line: Cubic approximation.

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Dimensionless intermolecular potential. Purple dashed line: Cubic approximation (adjusting the
amplitude of the oscillation).

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5. Conclusion
Sustained oscillating collisions between molecules, also denoted as molecular vibrations, have
usually been described by harmonic potentials [5]. However, the range of validity of the
harmonic or quadratic approximation is relatively narrow when common models of molecular
interaction are considered, like for example, the Lennard-Jones interaction model. In this case,
the harmonic approximation is valid up to only of the total potential well depth. A wider
range of validity is obtained by considering a cubic approximation to the interaction potential
(up to of the total potential well depth for the Lennard-Jones model).
Although the cubic model is a better approximation, the resulting differential equation (Eq.
3.32) does not provide a simple analytical solution for the dynamics of molecular position, as in
the case of the harmonic approximation. However, the molecular position under the cubic
potential can be further approximated by combining two exponential functions (Eq. 3.36).
The dynamic and spatial behavior of sustained oscillating collisions for different types of
potentials included the harmonic and cubic approximations, as well as the Lennard-Jones
model, were simulated for different conditions, and presented graphically.
Acknowledgments
This research did not receive any specific grant from funding agencies in the public,
commercial, or not-for-profit sectors.
References
[1] Hernandez, H. (2021). Collision Dynamics between Two Monoatomic Molecules. ForsChem
Research Reports, 6, 2021-13. doi: 10.13140/RG.2.2.29912.62726.
[2] Hernandez, H. (2017). Clausius’ sphere of action for different intermolecular potentials.
ForsChem Research Reports, 2, 2017-10. doi: 10.13140/RG.2.2.25246.23363.
[3] Halliday, D., Resnick, R., & Walker, J. (2018). Fundamentals of Physics. 11th Edition. John
Wiley & Sons, Inc., Hoboken (NJ). Section 15-1. pp. 413-421. https://www.wiley.com/en-
us/Fundamentals+of+Physics%3A+Extended%2C+11th+Edition-p-9781119306856.
[4] Lennard-Jones, J. E. (1931). Cohesion. Proceedings of the Physical Society, 43(5), 461. doi:
10.1088/0959-5309/43/5/301.
[5] Kestin, J., & Dorfman, J. R. (1971). A Course in Statistical Thermodynamics. Academic Press
Inc., New York. pp. 40-43. ISBN: 978-0-12-405350-2.

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Vol.

Sustained Oscillating Collisions between Two Monoatomic Molecules

Collision Dynamics, Cubic Approximation, Equations of Motion, Harmonic Potential,

16/09/2021 ForsChem Research Reports Vol. 6, 2021-14 (1 / 19)

2. Dynamics of Sustained Oscillating Collisions

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Figure 1. Schematic representation of the oscillating collision between two monoatomic

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Eq .(2.3) can also be alternatively expressed as follows:

3. Approximated Intermolecular Potentials

These conditions can be mathematically expressed by the following set of equations:

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The intermolecular potential function must be necessarily nonlinear, or otherwise, the

3.1. Quadratic (Harmonic) Potential

Then, conditions (3.1) to (3.6) become:

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Therefore, for the quadratic potential, Eq. (2.3) becomes:

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Furthermore, the dynamic behavior of the intermolecular potential is given by:

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Figure 2. Dynamic behavior of oscillating collisions for a quadratic intermolecular potential

Figure 3. Spatial behavior of oscillating collisions for a quadratic intermolecular potential

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3.2. Cubic Potential

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4. Lennard-Jones Intermolecular Potential Function

The Lennard-Jones intermolecular potential [4] can be expressed mathematically as follows:

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This expression is graphically represented in Figure 9, with the normalized intermolecular

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Figure 9. Relationship between the normalized intermolecular potential range ( ) and

As expected, the quadratic approximation only provides a reasonable fit ( ) for

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As an example, Figure 11 to Figure 16 show the simulation results of the Lennard-Jones

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