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A novel predictive model for formation enthalpies of Si and Ge hydrides with propane‐ and butane‐like structures
Author(s) -
Weng C.,
Kouvetakis J.,
Chizmeshya A. V. G.
Publication year - 2010
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/jcc.21662
Subject(s) - propane , butane , thermochemistry , standard enthalpy of formation , atom (system on chip) , enthalpy , chemistry , atom economy , metastability , thermodynamics , basis set , computational chemistry , density functional theory , computer science , organic chemistry , catalysis , physics , embedded system
Butane‐ and propane‐like silicon–germanium hydrides and chlorinated derivatives represent a new class of precursors for the fabrication of novel metastable materials at low‐temperature regimes compatible with selective growth and commensurate with the emerging demand for the reduced thermal budgets of complementary metal oxide semiconductor integration. However, predictive simulation studies of the growth process and reaction mechanisms of these new compounds, needed to accelerate their deployment and fine‐tune the unprecedented low‐temperature and low‐pressure synthesis protocols, require experimental thermodynamic data, which are currently unavailable. Furthermore, traditional quantum chemistry approaches lack the accuracy needed to treat large molecules containing third‐row elements such as Ge. Accordingly, here we develop a method to accurately predict the formation enthalpy of these compounds using atom‐wise corrections for Si, Ge, Cl, and H. For a test set of 15 well‐known hydrides of Si and Ge and their chlorides, such as Si 3 H 8 , Ge 2 H 6 , SiGeH 6 , SiHCl 3 , and GeCl 4 , our approach reduces the deviations between the experimental and predicted formation enthalpies obtained from complete basis set (CBS‐QB3), G2, and B3LPY thermochemistry to levels of 1–3 kcal/mol, or a factor of ∼5 over the corresponding uncorrected values. We show that our approach yields results comparable or better than those obtained using homodesmic reactions while circumventing the need for thermochemical data of the associated reaction species. Optimized atom‐wise corrections are then used to generate accurate enthalpies of formation for 39 pure Si‐Ge hydrides and a selected group of 20 chlorinated analogs, of which some have recently been synthesized for the first time. Our corrected enthalpies perfectly reproduce the experimental stability trends of heavy butane‐like compounds containing Ge. This is in contrast to the direct application of the CBS‐QB3 method, which yields erratic predictions. Our approach also provides quantitative bond‐additivity rules for the chlorination of these heavier species. Finally, we discuss structure and bonding trends across the entire sequence of butane‐, propane‐, and ethane‐like molecules with a special focus on the isomeric variations. © 2010 Wiley Periodicals, Inc. J Comput Chem, 2011