TY - JOUR
T1 - Computational Thermochemistry of Mono- and Dinuclear Tin Alkyls Used in Vapor Deposition Processes
AU - Harkins, Robin P.
AU - Cramer, Christopher J.
AU - Gladfelter, Wayne L.
N1 - Publisher Copyright:
© 2019 American Chemical Society.
PY - 2019/2/21
Y1 - 2019/2/21
N2 - 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 monotin- and ditin-containing molecules bearing hydrido and/or carbon-based ligands was generated, and their structures were optimized using density functional theory. On the basis of 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 (298-5000 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.
AB - 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 monotin- and ditin-containing molecules bearing hydrido and/or carbon-based ligands was generated, and their structures were optimized using density functional theory. On the basis of 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 (298-5000 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.
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U2 - 10.1021/acs.jpca.8b12072
DO - 10.1021/acs.jpca.8b12072
M3 - Article
C2 - 30746944
AN - SCOPUS:85061917359
SN - 1089-5639
VL - 123
SP - 1451
EP - 1460
JO - Journal of Physical Chemistry A
JF - Journal of Physical Chemistry A
IS - 7
ER -