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I'm conducting a molecular dynamics simulation for silica. Some time ago I turned to the fluctuating dipole model, and after much effort I'm still having problems implementing it.

In short, all oxygen atoms in the system are polarizable, and their dipole moments depend on their position with respect to all the other atoms in the system. More particularly, I use TS potential (http://digitallibrary.sissa.it/bitstream/handle/1963/2874/tangney.pdf?sequence=2), where dipoles are found iteratively at each time step.

This means that when evaluating forces acting on atoms, I have to take into account this potential energy dependency on coordinates. Before, I was using simple pairwise potential models, and so I would set my program to compute forces using analytic formulas obtained by differentiating potential energy expression.

Now I'm at a loss: how to implement this new potential? In all the articles that I've found they only give you formulas, but not the algorithm. As I see it, when I compute forces, acting on a certain atom, I have to take into account the change of the dipole of this atom, the change of dipoles of all the neighboring atoms, then tge change of dipoles of still more atoms, and so on, as they depend on each other. After all, it is because of this interdependency that the dipoles are found iteratively at each time step. Clearly, I can't compute forces iteratively for each atom, because the computational complexity of the algorithm would be way too high. Should I use some simple functions to account for the change of dipoles? This doesn't look like a good idea either, cause dipoles are calculated iteratively, with high precision, and then, where it actually matters (computing forces), we would use crude functions?

So how do I implement this model? Also, is it possible to compute forces analytically, as I did before, or is it necessary to compute them using finite difference formula for derivative?

I haven't found the answer for my question in literature, but if you know some article, or site, or book, where this material is highlighted, please, direct me to that source.

Thank you for your time!

Update:

Thank you for your answer. Unfortunately, this was not my question. I didn't ask how to compute dipoles, but how to compute forces given that those dipoles vary with movement considerably.

The straightforward way to compute them doesn't account for that dependence. In fact, I tried to compute forces in straightforward manner, but the results I got were not physically correct.

To analyze the situation, I set up a simulation of a system consisting of just two atoms: Si and O. They have opposite charges, and so they oscillate. And the energy time dependence graphic looks like this:

http://yadi.sk/d/9IfGEouw58I4c

(sorry for the link, it appears that I don't have enough points to post pictures yet)

The curve on the top represents kinetic energy, the one in the middle represents potential energy without taking dipole interaction into account, and the one at the bottom represents potential energy of the system, where dipole interaction was taken into account.

You can clearly see from this graphic, that the system is doing what it shouldn't do: climbing up the potential slope. So I decided this is due to the fact that I didn't take dipole moment coordinate dependence into account. For instance, at a given time point, we compute the forces, and they are directed so as to move both atoms toward each other. But when we do move them towards each other (even slightly), the dipole moment changes, and we find out that we actually ended up with higher potential energy than before! During the next time step the situation is the same.

So the question is, how to take this effect into account, cause what few ways I can think of are either way too computationally intense, or way too crude.

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This link points to a thesis that contains an otherwise unpublished chapter (chapter 6) on the simulation of a droplet of water on graphite using a force field that includes a linear response model for the dipole moment.

A lot of the approach is based on the following publication:

Abdolnour Toukmaji, Celeste Sagui, John Board, and Tom Darden. Efficient particle-mesh Ewald based approach to fixed and induced dipolar interactions. J. Chem. Phys., 113(24):10913–10927, 2000.

The approach is very crude / brute force:

  1. Perform one step of MD
  2. Calculate electrical field ($E_0$) using charges and old dipoles ($d_0$)
  3. From electrical field ($E_0$) calculate new dipoles ($d_1$)
  4. Check on convergence by comparing change in dipole moments ($d_1$ vs $d_0$)
  5. Calculate electrical field ($E_1$) using charges and new dipoles ($d_1$)
  6. From electrical field ($E_1$) calculate new dipoles ($d_2$)
  7. Check on convergence ($d_2$ vs. $d_1$)
  8. Repeat until convergence is reached

Convergence was not great and if I recall correctly it took about 5-10 iterations until the dipole moments had converged ...

Once you have the electrical field, the forces are straight forward..

Hope this helps, best regards urs

Update 1:

Indeed I did not understand your question correctly. Can you give me some more information:

  1. Can you provide me with information about the distance between the two ions at $t=0$, $t=330$ and $t=660$ (at the start and at the first two minima of kinetic energy)? The following comments are based on the assumption that the distance at $t=0$ is larger than at $t=330$, i.e. the ions start some distance apart and first move closer together. Can you confirm this?

  2. You state the bottom line is potential energy with dipole interaction. However, you make no reference to dipole-charge interaction? Did you include it in your potential energy calculation?

  3. You do not make any reference to polarisation energy? Did you include that in your potential energy computation?

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  • $\begingroup$ Thank you for your answer. Unfortunately, that wasn't my question. I updated my post to make the matter more clear. $\endgroup$ – Denis May 24 '13 at 14:54
  • $\begingroup$ 1. Yes, your assumption is correct. You can access the animation via this link: yadi.sk/d/5tFvqKAx5Ap_I. 2. Yes, I take dipole-charge interaction into account. In fact, this is the only type of dipole interaction in this system, since Si atom is not polarizable in the TS model. 3. No, there's no polarization energy in this model... One more significant detail: the model I use includes dipole dumping when O atoms are close to Si atoms, else polarization forces overcome Coulomb forces, and atoms merge or explode. $\endgroup$ – Denis May 26 '13 at 9:04
  • $\begingroup$ This dipole moment dumping, however, has a physical background, in a sense that it represents influence of Pauli principle on dipoles, when atoms come close enough for their electronic orbits to overlap. $\endgroup$ – Denis May 26 '13 at 9:08

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