Slides

Example 1.1: Lennard-Jones Potential

A NumFys Example
http://www.numfys.net

Fall 2012

A NumFys Example Example 1.1: Lennard-Jones Potential

www.numfys.net

Slides

p.1

Introduction to the Lennard-Jones Potential

The Lennard-Jones potential (also referred to as the L-J potential or 12-6 potential) is a simple physical model that approximates the interaction between a pair of neutral atoms or molecules. The most common expressions the L-J potential are: for VLJ =4 r
12 6 12 6

= rm r

rm 2 r

, (1)

where r is the distance between the particles. Here, is the depth (i.e. the minimum) of the potential well, reached at r = rm , and is the distance at which the inter-particle potential is zero. It can be shown that rm = 21/6 .
A NumFys Example Example 1.1: Lennard-Jones Potential www.numfys.net

Slides

p.2

The L-J Potential.

For = = 1, we obtain the following graph:

As we can see, we nd a global minimum and expect oscillations about this equilibrium as long as the total energy, Etotal = Ekin + Epot , does not exceed zero.
A NumFys Example Example 1.1: Lennard-Jones Potential www.numfys.net

Slides

p.3

Parameters for our Particular Example

In this example, we will consider the Lennard-Jones Potential for two H2 O molecules. The parameters are: = 0.32 109 m = 1.08 1021 J Note that the orientation-dependent interaction between the water dipoles is not included here explicitly.

A NumFys Example Example 1.1: Lennard-Jones Potential

www.numfys.net

Slides

p.4

Plot
We obtain this plot:

A NumFys Example Example 1.1: Lennard-Jones Potential

www.numfys.net

Slides

p.5

The Problem
We will now analyze oscillations about the equilibrium in a classical manner. First, we want to examine the frequency of small oscillations near r = rm . To do this, we approximate the force near r = rm . Thereafter, we want to compute the period of oscillations for larger perturbations when the linearization is a poor approximation.

A NumFys Example Example 1.1: Lennard-Jones Potential

www.numfys.net

Slides

p.6

Deriving the Force from the Potential

Let us calculate the force from the potential by taking the derivative of the potential: F (r ) = V (r ) = 12 rm 12 rm rm r rm r
13 13

(2) + rm r 12 rm
7

rm r

(3)

(4)

Note that F (rm ) = 0. Hence, r = rm is an equilibrium point. Now, we Taylor-expand the force about this equilibrium point.
A NumFys Example Example 1.1: Lennard-Jones Potential www.numfys.net

Slides

p.7

Approximating the Force near rm

We write F (rm + r ) F (rm ) + F (rm )r = 0 + F (rm )r Now, we need to determine F (rm ): rm 12 F (r ) = 2 13 r rm Substituting r = rm yields 72 rm 2 Using this result in equation (5), we nd the force near rm F (rm ) = F (rm + r ) 72 r rm 2 (7)
14 8

(5)

rm +7 r

(6)

(8)
www.numfys.net

A NumFys Example Example 1.1: Lennard-Jones Potential

Slides

p.8

The Frequency f of Small Oscillations

We can now compute the frequency of small oscillations about the equilibrium by writing 72 d 2 r = F ( rm + r ) r , (9) 2 dt rm 2 where m is the effective mass of the water-water molecule system. This describes harmonic oscillations with a frequency 72 2 = (2 f )2 = . (10) mrm 2 m Using the values for and rm = 21/6 from above, and m 9mproton , we obtain a frequency f = 1 = 2 2 72 = 1.01 1012 Hz 2 mrm (11)
www.numfys.net

A NumFys Example Example 1.1: Lennard-Jones Potential

Slides

p.9

Expanding the Problem

So far, we have examined the frequency near r = rm where the dynamics can be approximated by that of a harmonic oscillator. This was simple and we did not need any computational tools. However, what happens if we look at oscillations further away from r = rm ? If we look at our plot of the L-J potential, we can see that the graph is not symmetric about the equilibrium. During oscillations, we would expect the molecules to spend more time to the right of the equilibrium (r > rm ) then to the left of it. Let us study this phenomenon numerically.

A NumFys Example Example 1.1: Lennard-Jones Potential

www.numfys.net

Slides

p.10

Nonlinear Oscillations
Now, we will solve the exact dynamic equation m r = F (r ), where dots indicate time derivatives. We transform this ODE into a set of rst-order ODEs and employ Eulers method to solve it. We do this by introducing . Substitution into new variables v and w , with v = r and w = r the equation above gives 12 F (v ) = = w r= m mrm rm v
13

(12)

rm v

(13)

A NumFys Example Example 1.1: Lennard-Jones Potential

www.numfys.net

Slides

p.11

Euler Method: Set of Equations

This gives us the following set of equations v w = w, = 12 mrm rm v
13

(14) rm v
7

(15)

For our initial conditions, we choose v (0) = rm and w (0) > 0. Following our notation in Module 4.1, we can now write the Euler method as (v1 = v (0), w1 = w (0)) vn+1 = vn + h wn , wn+1
A NumFys Example Example 1.1: Lennard-Jones Potential

(16) rm vn
13

12 = wn + h mrm

rm vn

(17)
www.numfys.net

Slides

p.12

Implementation in Matlab
We can implement this in a simple for-loop in Matlab (see corresponding script):

The step size is chosen to be h = 1015 s.

A NumFys Example Example 1.1: Lennard-Jones Potential

www.numfys.net

Slides

p.13

Oscillations near r = rm
2 First, we set 1 2 mw0 = 0.001 . This corresponds to very small oscillations because the kinetic energy is much smaller than and, therefore, we are deep down in the potential well where the oscillations are harmonic. We plot the vector v which represents the position of the molecule vs. time steps.

A NumFys Example Example 1.1: Lennard-Jones Potential

www.numfys.net

Slides

p.14

Oscillations near r = rm

We nd the following features. The oscillations around the equilibrium r = rm seem harmonic. Matlab uses around 1000 time steps of magnitude 1015 s. Hence, the period is about T = 1000 1015 s = 1012 s, in agreement with our linear analysis.

A NumFys Example Example 1.1: Lennard-Jones Potential

www.numfys.net

Slides

p.15

Oscillations further up the Potential Well

Now lets see what the oscillations look like when we add 2 kinetic energy. We set 1 2 mw0 = 0.3 and n = 1270. We have to increase the number of time steps n because we expect the period to be longer.

A NumFys Example Example 1.1: Lennard-Jones Potential

www.numfys.net

Slides

p.16

Oscillations further up the Potential Well

We can clearly see how the molecule spends more time on the right side (r > rm ) of the potential well which we expected from the L-J plot. In this case, the period is about T = 1270 1015 s. Since T increases with the amplitude, we have no longer harmonic oscillations. Note that we treat this microscopic system classically and not quantum mechanically. However, it gives us some ideas about how a full quantum mechanical treatment would differ from that of a quantum mechanical harmonic oscillator.

A NumFys Example Example 1.1: Lennard-Jones Potential

www.numfys.net

Slides

p.17

Repeating Oscillations

So far, we have only looked at oscillations for one period. If we increase the number of oscillations, we would expect neither diminishing nor increasing amplitudes since energy is conserved. Unfortunately, Eulers method contains errors which can be large enough to clearly violate energy conservation in our solution. Hence, the amplitude may not be constant.

A NumFys Example Example 1.1: Lennard-Jones Potential

www.numfys.net

Slides

p.18

Plot: Repeating Oscillations

As the number of oscillations increases, the molecules move further away from equilibrium with each oscillation which would correspond to an increase in energy.
A NumFys Example Example 1.1: Lennard-Jones Potential www.numfys.net

Slides

p.19

Error in the Euler Method

Remember that this method is an approximation of the solution. Each time we calculate a new step, we make an error. This error results in an increase in the amplitude of each new oscillation. The error can be reduced by using better but more complicated approximations, or by reducing the step size h. In the next plot, we have reduced the step size to h = 1016 s. We have to increase the number of calculations to n = 100 000 so as to obtain the same amount of oscillations. This demands more computational time but reduces the error.

A NumFys Example Example 1.1: Lennard-Jones Potential

www.numfys.net

Slides

p.20

A Better But More Demanding Plot

A NumFys Example Example 1.1: Lennard-Jones Potential

www.numfys.net