jp057467m_si_001.pdf (231.72 kB)
BAC-MP4 Predictions of Thermochemistry for Gas-Phase Antimony Compounds in the Sb−H−C−O−Cl System
journal contributionposted on 2006-05-04, 00:00 authored by Andrew J. Skulan, Ida M. B. Nielsen, Carl F. Melius, Mark D. Allendorf
Calibrated by both experimental data and high-level coupled-cluster calculations, the BAC-MP4 methodology was applied to 51 SbLn (L = H, CH3, C2H5, Cl, and OH, n = 1−5) molecules, providing calculated heats of formation and associated thermodynamic parameters. These data identify a linear variation in heats of formation with ligand substitution, trends in bond dissociation energies (BDEs) with ligand identity [BDE(Sb−C2H5) < BDE(Sb−CH3) < BDE(Sb−H) < BDE(Sb−Cl) < BDE(Sb−OH)], and a monotonic decrease in BDE upon successive ligand elimination. The linear variation in BDE is consistent with the behavior of other group V elements, in contrast to the characteristic high−low−high trend of adjacent group III (In) and group IV (Sn) elements. Additionally, these data complement those of previous studies of metal−organic species and provide a foundation of thermochemical data that can aid in the selection of CVD precursors and deposition conditions for the growth of antimony-containing materials.