Mean square displacement

From Eq. (10.71) in the book “Thermodynamics of Crystal”, atomic displacement, u, is written by

\[u^\alpha(jl,t) = \left(\frac{\hbar}{2Nm_j}\right)^{\frac{1}{2}} \sum_{\mathbf{q},\nu}\left[\omega_\nu(\mathbf{q})\right]^{-\frac{1}{2}} \left[\hat{a}_\nu(\mathbf{q})\exp(-i\omega_\nu(\mathbf{q})t)+ \hat{a}^\dagger_\nu(\mathbf{-q})\exp({i\omega_\nu(\mathbf{q})}t)\right] \exp({i\mathbf{q}\cdot\mathbf{r}(jl)}) e^\alpha_\nu(j,\mathbf{q})\]

where j and l are the labels for the j-th atomic position in the l-th unit cell, t is the time, \(\alpha\) is an axis (a Cartesian axis in the default behavior of phonopy), m is the atomic mass, N is the number of the unit cells, \(\mathbf{q}\) is the wave vector, \(\nu\) is the index of phonon mode. e is the polarization vector of the atom jl and the band \(\nu\) at \(\mathbf{q}\). \(\mathbf{r}(jl)\) is the atomic position and \(\omega\) is the phonon frequency. \(\hat{a}^\dagger\) and \(\hat{a}\) are the creation and annihilation operators of phonon. The expectation value of the squared atomic displacement is calculated as,

\[\left\langle |u^\alpha(jl, t)|^2 \right\rangle = \frac{\hbar}{2Nm_j} \sum_{\mathbf{q},\nu}\omega_\nu(\mathbf{q})^{-1} (1+2n_\nu(\mathbf{q},T))|e^\alpha_\nu(j,\mathbf{q})|^2,\]

where \(n_\nu(\mathbf{q},T)\) is the phonon population, which is give by,

\[n_\nu(\mathbf{q},T) = \frac{1}{\exp(\hbar\omega_\nu(\mathbf{q})/\mathrm{k_B}T)-1},\]

where T is the temperature, and \(\mathrm{k_B}\) is the Boltzmann constant. The equation is calculated using the commutation relation of the creation and annihilation operators and the expectation values of the combination of the operations, e.g.,

\[\begin{split}[ \hat{a}_\nu(\mathbf{q}), \hat{a}^\dagger_{\nu'}(\mathbf{q'}) ] &= \delta(\mathbf{q}-\mathbf{q}')\delta_{\nu\nu'},\\ [ \hat{a}_\nu(\mathbf{q}), \hat{a}_{\nu'}(\mathbf{q'}) ] &= 0,\\ [ \hat{a}^\dagger_\nu(\mathbf{q}), \hat{a}^\dagger_{\nu'}(\mathbf{q'}) ] &= 0,\\ \langle|\hat{a}_\nu(\mathbf{q})\hat{a}_{\nu'}(\mathbf{q'})|\rangle &= 0,\\ \langle|\hat{a}^\dagger_\nu(\mathbf{q})\hat{a}^\dagger_{\nu'}(\mathbf{q'})|\rangle &= 0.\end{split}\]

Mean square displacement matrix

Mean square displacement matrix is defined as follows:

\[\mathrm{U}_\text{cart}(j, T) = \frac{\hbar}{2Nm_j} \sum_{\mathbf{q},\nu}\omega_\nu(\mathbf{q},T)^{-1} (1+2n_\nu(\mathbf{q})) \mathbf{e}_\nu(j,\mathbf{q}) \otimes \mathbf{e}^*_\nu(j,\mathbf{q}).\]

This is a symmetry matrix and diagonal elements are same as mean square displacement calculated along Cartesian x, y, z directions.

Projection to an arbitrary axis from the Cartesian axes

In phonopy, eigenvectors are calculated in the Cartesian axes that are defined in the input structure file. Mean square displacement along an arbitrary axis is obtained projecting eigenvectors in the Cartesian axes as follows:

\[\left\langle |u(jl, t)|^2 \right\rangle = \frac{\hbar}{2Nm_j} \sum_{\mathbf{q},\nu}\omega_\nu(\mathbf{q})^{-1} (1+2n_\nu(\mathbf{q}))| \hat{\mathbf{n}}\cdot\mathbf{e}_\nu(j,\mathbf{q})|^2\]

where \(\hat{\mathbf{n}}\) is an arbitrary unit direction.

Mean square displacement matrix in cif format

According to the paper by Grosse-Kunstleve and Adams [J. Appl. Cryst., 35, 477-480 (2002)], mean square displacement matrix in the cif definition (aniso_U), \(\mathrm{U}_\text{cif}\), is obtained by

\[\mathrm{U}_\text{cif} = (\mathrm{AN})^{-1}\mathrm{U}_\text{cart} (\mathrm{AN})^{-\mathrm{T}},\]

where \(\mathrm{A}\) is the matrix to transform a point in fractional coordinates to the Cartesian coordinates and \(\mathrm{N}\) is the diagonal matrix made of reciprocal basis vector lengths as follows:

\[\begin{split}\mathrm{A} = \begin{pmatrix} a_x & b_x & c_x \\ a_y & b_y & c_y \\ a_z & b_z & c_z \end{pmatrix}\end{split}\]

and

\[\begin{split}\mathrm{N} = \begin{pmatrix} a^* & 0 & 0 \\ 0 & b^* & 0 \\ 0 & 0 & c^* \end{pmatrix}.\end{split}\]

\(a^*\), \(b^*\), \(c^*\) are defined without \(2\pi\).