Journal
COMPUTATIONAL AND THEORETICAL CHEMISTRY
Volume 1004, Issue -, Pages 61-68Publisher
ELSEVIER
DOI: 10.1016/j.comptc.2012.10.021
Keywords
Lead chlorides; Chloroplumbate anions; MP2/MP2(PCM); Thermodynamics; Kinetics; Vertical detachment energies
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Funding
- Polish State Funds for Scientific Research [DS/8220-4-0087-2, DS/8371-4-0137-2]
- Foundation for Polish Science
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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.
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