Computational Thermochemistry of Mono- and Dinuclear Tin Alkyls Used in Vapor Deposition Processes

Harkins, R.; Cramer, C. J.; Gladfelter, W. L.
J. Phys. Chem. A 2019, 123, 1451 (doi:10.1021/acs.jpca.8b12072).

Hexamethylditin has been reported to be a more effective precursor compared to monotin analogs in hybrid molecular beam epitaxy depositions of perovskite oxides. To understand the differences, a library of 68 mono- and ditin-containing molecules bearing hydrido and/or carbon-based ligands was generated, and their structures were optimized using density functional theory. Based on a modified W1-F12 composite thermochemical method, thermochemical data (enthalpy of formation, entropy, and heat capacity) were calculated for each structure over a range of temperatures (298 K-5000 K). The application of the modified W1-F12 method to heavy element compounds was benchmarked against existing experimental and computational studies of mononuclear hydrido, alkyl and mixed hydridoalkyl complexes of silicon, germanium and tin. The library of thermodynamic data was used in partial equilibrium calculations from 300 to 1500 K to determine gas phase compositions resulting from the pyrolysis of tetramethyltin and hexamethylditin at 10^-6 and 760 Torr.