在固态氩中M(OH)(1,2,4)（M = Pb，Sn）的红外光谱。

Infrared spectra of M(OH)(1,2,4) (M = Pb, Sn) in solid argon.

作者信息

Wang Xuefeng, Andrews Lester

机构信息

Chemistry Department, University of Virginia, Charlottesville, Virginia 22904-4319, USA.

出版信息

J Phys Chem A. 2005 Oct 13;109(40):9013-20. doi: 10.1021/jp053420p.

DOI:10.1021/jp053420p

PMID:16332006

Abstract

Infrared absorptions for the matrix-isolated lead and tin hydroxides M(OH), M(OH)2 and M(OH)4 (M = Pb, Sn) were observed in laser-ablated metal atom reactions with H2O2 during condensation in excess argon. The major M(OH)2 product was also observed with H2 and O2 mixtures, which allowed the substitution of 18O2. The band assignments were confirmed by appropriate D2O2, D2, 16O18O, and 18O2 isotopic shifts. MP2 and B3LYP calculations were performed to obtain molecular structures and to reproduce the infrared spectra. The minimum energy structure found for M(OH)2 has C(s) symmetry and a weak intramolecular hydrogen bond. In experiments with Sn, HD, and O2, the internal D bond is favored over the H bond for Sn(OH)(OD). The Pb(OH)4 and Sn(OH)4 molecules are calculated to have S4 symmetry and substantial covalent character.

摘要

在过量氩气冷凝过程中，通过激光烧蚀金属原子与过氧化氢的反应，观察到了基质隔离的氢氧化铅和氢氧化锡M(OH)、M(OH)₂和M(OH)₄（M = Pb、Sn）的红外吸收。在氢气和氧气混合物反应中也观察到了主要产物M(OH)₂，这使得可以用¹⁸O₂进行取代。通过适当的D₂O₂、D₂、¹⁶O¹⁸O和¹⁸O₂同位素位移证实了谱带归属。进行了MP2和B3LYP计算以获得分子结构并重现红外光谱。发现M(OH)₂的最低能量结构具有C(s)对称性和弱分子内氢键。在锡、HD和氧气的实验中，对于Sn(OH)(OD)，内部D键比H键更受青睐。计算得出Pb(OH)₄和Sn(OH)₄分子具有S₄对称性和显著的共价特性。