Reactions of M+ and MO+(M = V, Nb, Ta) with methanol

被引：26

作者：

Cao, YL

Zhao, XA

Xin, B

Xiong, SX

Tang, ZC ^{[1
]}

机构：

[1] Chinese Acad Sci, Inst Chem, State Key Lab Mol React Dynam, Beijing 100080, Peoples R China

[2] Chinese Acad Sci, Inst Chem, Ctr Mass Spect, Beijing 100080, Peoples R China

来源：

JOURNAL OF MOLECULAR STRUCTURE-THEOCHEM | 2004年 / 683卷 / 1-3期

基金：

中国国家自然科学基金;

关键词：

transition state; DFT; reaction pathway;

D O I：

10.1016/j.theochem.2004.06.001

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：

The primary reactions of the transition metal cations M+ (M = V, Nb and Ta) and their oxides with methanol are experimentally and theoretically investigated. Combining with the experimental results, we propose the reaction pathways of those primary reactions. The potential energy surfaces (PES) of these reactions are explored at B3LYP/Lanl2dz (for M) and 6-31g* (for C, H and 0) level. The structures and properties of the complexes involving in these reactions are also theoretically studied. The calculated results show that a crossing between the high-spin and low-spin PES occurs just after TS1, which plays an important role in decreasing the barrier heights of these transition states. The theoretical results are in excellent agreement with the experimental results. (C) 2004 Elsevier B.V. All rights reserved.

引用

页码：141 / 146

页数：6

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