Theoretical investigation on the mechanism of LiH+NH3 → LiNH2+H2 reaction

被引：17

作者：

Kar, Tapas ^{[1
]}

Scheiner, Steve ^{[1
]}

Li, Leijun ^{[2
]}

机构：

[1] Utah State Univ, Dept Chem & Biochem, Logan, UT 84322 USA

[2] Utah State Univ, Dept Mech & Aerosp Engn, Logan, UT 84322 USA

来源：

JOURNAL OF MOLECULAR STRUCTURE-THEOCHEM | 2008年 / 857卷 / 1-3期

基金：

美国国家科学基金会;

关键词：

reaction mechanism; lithium amide formation; H-2; elimination; MP2/CCSD(T);

D O I：

10.1016/j.theochem.2008.02.010

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：

High level electronic structure calculations predict the molecular mechanism of H-2 elimination in the LiH + NH3 -> LiNH2 + H-2 reaction. Geometries and energies of stationary points are obtained using second-order perturbation theory (MP2) and coupled cluster CCSD(T) theory with the aug-cc-pVTZ basis set. The reaction proceeds via intermediate molecular LiNH4 complexes, namely HLi-NH3 (reactant side) and LiNH2-H-2 (product side). Each reactant contributes one H atom to the product H2. (c) 2008 Elsevier B.V. All rights reserved.

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页码：111 / 114

页数：4

相关论文

共 15 条

[1] Interaction between lithium amide and lithium hydride [J].

Chen, P ;

Xiong, ZT ;

Luo, JZ ;

Lin, JY ;

Tan, KL .

JOURNAL OF PHYSICAL CHEMISTRY B, 2003, 107 (39) :10967-10970

[2] Interaction of hydrogen with metal nitrides and imides [J].

Chen, P ;

Xiong, ZT ;

Luo, JZ ;

Lin, JY ;

Tan, KL .

NATURE, 2002, 420 (6913) :302-304

[3] GAUSSIAN-BASIS SETS FOR USE IN CORRELATED MOLECULAR CALCULATIONS .1. THE ATOMS BORON THROUGH NEON AND HYDROGEN [J].

DUNNING, TH .

JOURNAL OF CHEMICAL PHYSICS, 1989, 90 (02) :1007-1023

[4] THE PATH OF CHEMICAL-REACTIONS - THE IRC APPROACH [J].

FUKUI, K .

ACCOUNTS OF CHEMICAL RESEARCH, 1981, 14 (12) :363-368

[5] REACTION-PATH FOLLOWING IN MASS-WEIGHTED INTERNAL COORDINATES [J].

GONZALEZ, C ;

SCHLEGEL, HB .

JOURNAL OF PHYSICAL CHEMISTRY, 1990, 94 (14) :5523-5527

[6] First synthesis and structural determination of a monomeric, unsolvated lithium amide, LiNH2 [J].

Grotjahn, DB ;

Sheridan, PM ;

Al Jihad, I ;

Ziurys, LM .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2001, 123 (23) :5489-5494

[7]

Hehre WJ., 1986, Ab Initio Molecular Orbital Theory

[8] Ultrafast reaction between LiH and NH3 during H2 storage in Li3N [J].

Hu, YH ;

Ruckenstein, E .

JOURNAL OF PHYSICAL CHEMISTRY A, 2003, 107 (46) :9737-9739

[9] Mechanism of novel reaction from LiNH2 and LiH to Li2NH and H2 as a promising hydrogen storage system [J].

Ichikawa, T ;

Hanada, N ;

Isobe, S ;

Leng, HY ;

Fujii, H .

JOURNAL OF PHYSICAL CHEMISTRY B, 2004, 108 (23) :7887-7892

[10] Hydrogen desorption mechanism in a Li-N-H system by means of the isotopic exchange technique [J].

Isobe, S ;

Ichikawa, T ;

Hino, S ;

Fujii, H .

JOURNAL OF PHYSICAL CHEMISTRY B, 2005, 109 (31) :14855-14858