I am trying to understand what the mean field approximation means when expressed in tensor notation for the Maier-Saupe Model of nematic liquid crystals. I am following along with Jonathan Selinger's lecture and my question appears around 16 mins in. The system in question is a system of cylindric molecules orientationaly aligned along a director. My confusion arises from how the angular dependence of this potential is expressed and how the mean field approximation is made concerning this angle.
To begin with, we have pairwise interaction energy: $$ V_{int} = -J P_2(\cos(\gamma)) = -J(\frac{3}{2}\cos^2\gamma - \frac{1}{2})$$
where J is the coupling strength of the interaction and $\gamma$ is the angle between the cylindrical molecules.
This pairwise interaction energy is an anisotropic potential which pushes the molecules to align with one another. Given this interaction potential, we want to calculate the free energy of the system with respect to an order parameter to see if the system is isotropic or nematic for a given temperature.
To calculate the free energy $F = \langle E \rangle - TS$, we take the average of the internal energy
$$ \langle E \rangle = - J \frac{Nq}{2} \langle \frac{3}{2}\cos^2\gamma - \frac{1}{2} \rangle$$
Where $\langle E \rangle $ denotes the average internal energy and $\frac{Nq}{2}$ is the number of interacting pairs. The cosine squared term is then expressed as a dot product of the two unit vectors of each molecule, $\hat{l}$ and $\hat{m}$, and that dot product is then expressed in Einstein summation notation for tensors, which is still fine with me:
$$ \langle \frac{3}{2}\cos^2\gamma - \frac{1}{2} \rangle = \langle \frac{3}{2}(\hat{l} \cdot \hat{m})^2 - \frac{1}{2} \rangle = [ \frac{3}{2} \langle l_im_il_jm_j \rangle - \frac{1}{2}]$$.
My issue is with the next step. Now, Selinger breaks up this average of products into a product of averages. However, it is broken so that only terms from one molecule are multiplied by another:
$$\langle l_im_il_jm_j \rangle = \langle l_il_j \rangle \langle m_im_j\rangle $$
So he says here that this is the mean field approximation. That mathematically this is equivalent to assuming the molecules are uncorrelated with one another. Then once breaks things up into these outer products, it is easy to relate these outer products to the nematic order parameter of the Q tensor, and do the desired analysis.
My questions are:
- How does this final step correspond to making a mean field approximation?
- If this is just an approximate formula, what would the full formula be for this step? I would really appreciate being able to to explicitly see what terms we are neglecting with this approximation.
- If I understand correctly,$\langle l_il_j \rangle \langle m_im_j \rangle$ just implies regular old matrix multiplication here to generate a 3x3 tensor. How are we taking a scalar (the cosine squared of the intermolecular angle) and approximating this with a 3x3 tensor?
The explanation Selinger gives for this step is related to the mean field approximation of the Ising model, where he draws a connection between the approximation in the Ising model, where $\pm 1 = \sigma_i$ for the spin at site i, and the mean field approximation is expressed as $\langle \sigma_i \sigma_j \rangle = \langle \sigma_i \rangle \langle \sigma_j \rangle$.
These notes draw a connection between this approximation and the covariance/Pearson correlation coefficient where $\rho(X,Y) = \frac{Cov(X,Y)}{\sigma_x \sigma_y} = \frac{\langle XY \rangle - \langle X \rangle \langle Y \rangle}{\sigma_x \sigma_y} $ where $\sigma_x$ is now the std dev of x and $\rho(X,Y)$ the pearson correlation coefficient. He points out if $\rho(X,Y) = 0$ the two variables are said to be "uncorrelated" which implies $ \langle XY \rangle - \langle X \rangle \langle Y \rangle = 0 \rightarrow \langle XY \rangle = \langle X \rangle \langle Y \rangle$, which has the form of the approximation we are making. However, even given this level of explanation, it is still not clear to me (1) how this formula relates to the tensor manipulations above and (2) how saying the two molecule's orientations are uncorrelated corresponds to the physical intuition behind the mean field approximation, that being that you are "averaging out" all the interactions felt by one molecule into a single field of interaction for that molecule. Wouldn't this average field still cause some correlation in the orientations of the molecules? Indeed isn't that the point of this method - to generate an average potential which causes the orientations to be correlated with one another along a director to generate a nematic phase?