Chemically Accurate Thermochemistry of Cadmium: An ab Initio Study of Cd + XY (X = H, O, Cl, Br; Y = Cl, Br)

详细信息    查看全文

• 作者：Benjamin C. Shepler ; Kirk A. Peterson
• 刊名：Journal of Physical Chemistry A
• 出版年：2006
• 出版时间：November 9, 2006
• 年：2006
• 卷：110
• 期：44
• 页码：12321 - 12329
• 全文大小：75K
• 年卷期：v.110,no.44(November 9, 2006)
• ISSN：1520-5215

文摘

Using a composite coupled cluster method employing sequences of correlation consistent basis sets for completebasis set (CBS) extrapolations and with explicit treatment of core-valence correlation and scalar and spin-orbit relativistic effects, the 0 K enthalpies of a wide range of cadmium-halide reactions, namely, Cd +(HCl, HBr, ClO, BrO, Cl₂, BrCl, Br₂) have been determined to an estimated accuracy of ±1 kcal/mol. Inaddition, accurate equilibrium geometries, harmonic frequencies, and dissociation energies have been calculatedat the same level of theory for all the diatomic (e.g., CdH, CdO, CdCl, CdBr) and triatomic (CdHCl, CdHBr,CdClO, CdBrO, CdCl₂, CdBrCl, CdBr₂) species involved in these reactions, some for the very first time.Like their mercury analogues, all of the abstraction reactions are predicted to be endothermic, while theinsertion reactions are strongly exothermic with the formation of stable linear, Cd-centric complexes. Withthe exception of CdH and the reactions involving this species, the present results for the remaining Cd-containing systems are believed to be the most accurate to date.