标题:The degree of proton transfer for XH???NH_3 (X = F, Br, HS, and HCOO) heterodimers upon attachment of an excess electron
作者:Lihua Dong;Jinhu Wang
作者机构:School of Chemical Engineering, Taishan Medical University, Taian, Shandong 271000, China;School of Chemistry and Chemical Engin
来源:Computational & theoretical chemistry
出版年:2012
页码:95-100
关键词:Excess electron;Barrier-free proton transfer (BFPT);Vertical detachment energy (VDE);Potential energy surfaces (PESs)
摘要:A DFT method is employed to elucidate the degree of proton transfer (PT) for XH???NH_3 (X = F, Br, HS, and HCOO) heterodimers upon an excess electron attachment. Only the anionic complex of (BrH???NH_3)~- has an intermolecular barrier-free proton transfer (BFPT) with a larger vertical detachment energy (VDE) of 16.60 kcal/mol. The anionic complexes without BFPT have only one (F—H???NH_3~- and HCOO—H???NH_3~-) or two minima (HS—H???NH_3~- and HS—NH_4~+) in the potential energy surfaces (PESs). In the latter case, there is a transition state with an energy barrier of 1.76 kcal/mol. When solvent is considered as the environmental conditions, intermolecular PT occurs for anionic complexes of (H_2O)n(FH???NH3)~- and (H_2O)n(HCOOH???NH_3)~-. The minimum number of water molecules is three for the former and two for the latter respectively.
资源类型:期刊论文
TOP