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Stabilized Nitrogen Framework Anions in the Ga–N System

MetadataDetails
Publication Date2022-11-17
JournalJournal of the American Chemical Society
AuthorsHang Zhai, Rui Xu, Jianhong Dai, Xiaoli Ma, Xiaohui Yu
InstitutionsJilin University, Songshan Lake Materials Laboratory
Citations37

Nitrogen-rich compounds have attracted significant fundamental and practical interest owing to their ability to accommodate diverse nitrogen-bonding patterns and their feasibility as high-energy-density materials. Herein, we examine a wide range of chemical compositions in the compressed Ga-N system using first-principles structural search and experimental preparation using a laser-heated diamond anvil cell. Our investigations have theoretically identified three thermodynamically stable stoichiometries─GaN<sub>15</sub>, GaN<sub>10</sub>, and GaN<sub>5</sub>─with surprisingly versatile polymeric nitrogen framework topologies. Strikingly, our results show that the required synthetic pressures for forming polymeric nitrogen phases in GaN<sub>10</sub> and GaN<sub>5</sub> are much lower than that for pure solid nitrogen. Finally, we evaluated the energy involved in decomposing the compounds and validated that they are promising candidates for high-energy-density materials. These findings have broad implications for designing and synthesizing novel nitrogen-rich compounds through the reaction between p electron elements and nitrogen at modest pressures and for nitrogen chemistry under extreme conditions.