Rigid unit modes

Rigid unit modes (RUMs) represent a class of lattice vibrations or phonons that exist in network materials such as quartz, cristobalite or zirconium tungstate. Network materials can be described as three-dimensional networks of polyhedral groups of atoms such as SiO4 tetrahedra or TiO6 octahedra. A RUM is a lattice vibration in which the polyhedra are able to move, by translation and/or rotation, without distorting. RUMs in crystalline materials are the counterparts of floppy modes in glasses, as introduced by Jim Phillips and Mike Thorpe. Rigid unit modes (RUMs) represent a class of lattice vibrations or phonons that exist in network materials such as quartz, cristobalite or zirconium tungstate. Network materials can be described as three-dimensional networks of polyhedral groups of atoms such as SiO4 tetrahedra or TiO6 octahedra. A RUM is a lattice vibration in which the polyhedra are able to move, by translation and/or rotation, without distorting. RUMs in crystalline materials are the counterparts of floppy modes in glasses, as introduced by Jim Phillips and Mike Thorpe. The idea of rigid unit modes was developed for crystalline materials to enable an understanding of the origin of displacive phase transitions in materials such as silicates, which can be described as infinite three-dimensional networks of corner-lined SiO4 and AlO4 tetrahedra. The idea was that rigid unit modes could act as the soft modes for displacive phase transitions. The original work in silicates showed that many of the phase transitions in silicates could be understood in terms of soft modes that are RUMs. After the original work on displacive phase transitions, the RUM model was also applied to understanding the nature of the disordered high-temperature phases of materials such as cristobalite, the dynamics and localised structural distortions in zeolites, and negative thermal expansion. The simplest way to understand the origin of RUMs is to consider the balance between the numbers of constraints and degrees of freedom of the network, an engineering analysis that dates back to James Clerk Maxwell and which was introduced to amorphous materials by Jim Phillips and Mike Thorpe. If the number of constraints exceeds the number of degrees of freedom, the structure will be rigid. On the other hand, if the number of degrees of freedom exceeds the number of constraints, the structure will be floppy. For a structure that consists of corner-linked tetrahedra (such as the SiO4 tetrahedra in silica, SiO2) we can count the numbers of constraints and degrees of freedom as follows. For a given tetrahedron, the position of any corner has to have its three spatial coordinates (x,y,z) match the spatial coordinates of the corresponding corner of a linked tetrahedron. Thus each corner has three constraints. These are shared by the two linked tetrahedra, so contribute 1.5 constraints to each tetrahedron. There are 4 corners, so we have a total of 6 constraints per tetrahedron. A rigid three-dimensional object has 6 degrees of freedom, 3 translations and 3 rotations. Thus there is an exact balance between the numbers of constraints and degrees of freedom.