From Eq. (10.71) in the book “Thermodynamics of Crystal”, atomic displacement, u, is written by
where j and l are the labels for the j-th atomic position in the l-th unit cell, t is the time, 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, is the wave vector, is the index of phonon mode. e is the polarization vector of the atom jl and the band at . is the atomic position and is the phonon frequency. and are the creation and annihilation operators of phonon. The expectation value of the squared atomic displacement is calculated as,
where is the phonon population, which is give by,
where T is the temperature, and 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.,
Mean square displacement matrix is defined as follows:
This is a symmetry matrix and diagonal elements are same as mean square displacement calculated along Cartesian x, y, z directions.
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:
where is an arbitrary unit direction.
According to the paper by Grosse-Kunstleve and Adams [J. Appl. Cryst.,
35, 477-480 (2002)], mean square displacement matrix in the cif
, is obtained by
where is the matrix to transform a point in fractional coordinates to the Cartesian coordinates and is the diagonal matrix made of reciprocal basis vector lengths as follows:
, , are defined without .