Thermal and solvent effects on the coordination structure of LiA1H4:: a computational study

被引：8

作者：

Asciutto, E ^{[1
]}

Crespo, A ^{[1
]}

Estrin, DA ^{[1
]}

机构：

[1] Univ Buenos Aires, Fac Ciencias Exactas & Nat, Dept Quim Inorgan Analit & Quim Fis, INQUIMAE, Buenos Aires, DF, Argentina

来源：

CHEMICAL PHYSICS LETTERS | 2002年 / 353卷 / 1-2期

关键词：

D O I：

10.1016/S0009-2614(02)00006-4

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

We have characterized LiAlH4 and its dimer [LiAlH4](2) in vacuum and in solution using Hartree-Fock (HF), Moller-Plesset (MP2), and DFT electronic structure calculations coupled to the PCM solvation model. We found that the dimer is the most relevant species in vacuum but that a significant fraction of monomeric species may exist in solution. Monte Carlo simulations of isolated and solvated LiAlH4 have also been performed to investigate structural changes with temperature and solvation. The predominant species in both vacuum and solution simulations at 300 K was found to be the bidentate isomer, in agreement with the PCM calculations. (C) 2002 Elsevier Science B.V. All rights reserved.

引用

页码：178 / 184

页数：7

共 27 条

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Allen M. P., 1987, Computer Simulation of Liquids

[2] Convincing evidence, not involving cyclizable radical probes, that the reaction of LiAlH4 with hindered alkyl iodides proceeds predominantly by a single electron transfer pathway [J].