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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Unimolecular Reactions of Proton-Bound Cluster Ions: Competition between Dissociation and Isomerization in the Methanol-Acetonitrile Dimer
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Unimolecular Reactions of Proton-Bound Cluster Ions: Competition between Dissociation and Isomerization in the Methanol-Acetonitrile Dimer

机译：质子束缚簇离子的单分子反应：甲醇-乙腈二聚体中解离和异构化之间的竞争。

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摘要

The metastable proton-bound dimer of acetonitrile and methanol, (CH_3CN)(CH_3OH)H~+, exhibits two unimolecular reactions on the microsecond time scale, a simple bond cleavage reaction to form CH_3CNH~+ and CH_3OH, and the loss of water to form CH_3CNCH_3~+. The latter process is preceded by the isomerization of the proton-bound dimer to a second isomer, (CH_3CNCH_3)(H_2O)~+. Collision-induced dissociation mass spectrometry was used to identify the two sets of reaction products, and the results of isotopic labeling experiments suggest that there is a rate-limiting isomerization step going from the proton-bound dimer to the second complex. The competition between the two channels was modeled with ab initio calculations and RRKM rate theory to obtain relative energies for the reaction surface. The transition structure for the rate-determining isomerization could not be located with ab initio calculations, and so its relative energy was estimated using RRKM theory. The 0 K binding energy of the (CH_3CN)(CH_3OH)H~+ complex was calculated to be 121 kJ mol~(-1) at the G2 level of theory (relative to the dissociation products CH_3CNH~+ and CH_3OH).
机译：乙腈和甲醇的亚稳质子结合二聚体（CH_3CN）（CH_3OH）H〜+在微秒级上表现出两个单分子反应，一个简单的键裂解反应形成CH_3CNH〜+和CH_3OH，以及水失去形式为CH_3CNCH_3〜+。在后面的过程之前，质子结合的二聚体异构化为第二种异构体（CH_3CNCH_3）（H_2O）〜。碰撞诱导解离质谱用于鉴定两组反应产物，同位素标记实验的结果表明，从质子结合的二聚体到第二个络合物有一个限速异构化步骤。使用从头算和RRKM速率理论对两个通道之间的竞争进行建模，以获得反应表面的相对能量。不能从头算来确定速率决定异构化的过渡结构，因此使用RRKM理论估算其相对能量。在理论的G2水平下（相对于解离产物CH_3CNH〜+和CH_3OH），（CH_3CN）（CH_3OH）H〜+配合物的0 K结合能经计算为121 kJ mol〜（-1）。

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