Abstract
The lowest singlet and triplet potential energy surfaces for all group 15 HAsXH (X = N, P, As, Sb, and Bi) systems have been explored through ab initio calculations. The geometries of the various isomers were determined at the QCISD/LANL2DZdp level and confirmed to be minima by vibrational analysis. In the case of nitrogen, the global minimum is found to be a triplet H~2~NAs structure. For the phosphorus case, singlet trans‐HAsPH is found to be global minima surrounded by large activation barriers, so that it should be observable. For arsenic, theoretical investigations demonstrate that the stability of HAsAsH isomers decreases in the order singlet trans‐HAsAsH > triplet H~2~AsAs > singlet cis‐HAsAsH > triplet HAsAsH > singlet H~2~AsAs. For antimony and bismuth, the theoretical findings suggest that the stability of HAsXH (X = Sb and Bi) systems decreases in the order triplet H~2~AsX ≈ singlet trans‐HAsXH > singlet cis‐HAsXH > triplet HAsXH > triplet H~2~XAs > singlet H~2~AsX > singlet H~2~XAs. Our model calculations indicate that the relativistic effect on heavier group 15 elements should play an important role in determining the geometries as well as the stability of HAsXH molecules. The results obtained are in good agreement with the available experimental data and allow a number of predictions to be made. © 2008 Wiley Periodicals, Inc. J Comput Chem, 2008