期刊
COMPUTATIONAL AND THEORETICAL CHEMISTRY
卷 1004, 期 -, 页码 61-68出版社
ELSEVIER
DOI: 10.1016/j.comptc.2012.10.021
关键词
Lead chlorides; Chloroplumbate anions; MP2/MP2(PCM); Thermodynamics; Kinetics; Vertical detachment energies
资金
- Polish State Funds for Scientific Research [DS/8220-4-0087-2, DS/8371-4-0137-2]
- Foundation for Polish Science
Ab initio studies of the structure and physicochemical properties of lead chlorides (PbClx; x = 1 - 5) and their chloroplumbate derivatives (PbClyn-; y = 1 - 7, n = 1 - 4), as well as the thermodynamics and kinetics of processes involving these entities, were carried out at the MP2 and MP2(PCM) levels of theory. The following appeared to be electronically stable: isolated lead chlorides in which x = 1 5, singly charged anions (n = 1) in which x = 1 - 6 and doubly charged anions (n = 2) in which y = 4 6, and additionally PbCl53-, PbCl63-, PbCl64- and PbCl72- in the aqueous phase. Spontaneous reactions in the Pb/Cl-2/Cl- system led to PbClx (x = 1 - 4) and PbCly- (y = 2 - 5) in the gaseous phase, and also PbCly2- (y = 4 - 6), PbCly3- (y = 5,6) and PbCl64- in the aqueous phase. The attachment of Cl- to neutral molecules was free of any kinetic activation barrier, whereas attachment to anions required a moderate activation barrier to be overcome. Cl-2 reacts via a consecutive two-step process: complex formation, followed by unconcerted substitution. (C) 2012 Elsevier B.V. All rights reserved.
作者
我是这篇论文的作者
点击您的名字以认领此论文并将其添加到您的个人资料中。
推荐
暂无数据