Abstract
Whereas nearly all compounds obey Dalton’s rule of integer stoichiometry ( : , both integer), there is a class of systems, exemplified by the rocksalt structure , that exhibits large deviations from stoichiometry via vacancies, even at low temperatures. By combining first-principles total energy calculations with lattice statistical mechanics, we scan an astronomical number of possible structures, identifying the stable ground states. Surprisingly, all have the same motifs: (111) planes with (112) vacancy rows arranged in (110) columns. Electronic structure calculations of the ground states (identified out of structures) reveal the remarkable origins of nonstoichiometry.
- Received 13 August 2001
DOI:https://doi.org/10.1103/PhysRevLett.87.275508
©2001 American Physical Society