Origin of the exceptional negative thermal expansion in metal-organic framework-5 Zn4O(1,4-benzenedicarboxylate)3

Metal organic framework-5 (MOF-5) was recently suggested to possess an exceptionally large negative thermal-expansion coefficient. Our direct experimental measurement of the thermal expansion of MOF-5 using neutron powder diffraction, in the temperature range of 4 to 600 K, shows that the linear thermal-expansion coefficient is approximate to-16 X 10(-6) K-1. To understand the origin of this large negative thermal-expansion behavior, we performed first-principles lattice dynamics calculations. The calculated thermal-expansion coefficients within quasiharmonic approximation agree well with the experimental data. We found that almost all low-frequency lattice vibrational modes (below similar to 23 meV) involve the motion of the benzene rings and the ZnO4 clusters as rigid units and the carboxyl groups as bridges. These so-called "rigid-unit modes" exhibit various degrees of phonon softening (i.e., the vibrational energy decreases with contracting crystal lattice) and thus are directly responsible for the large negative thermal expansion in MOF-5. Initial efforts were made to observe the phonon softening experimentally.