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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Interconversion of ROC~+ and RCO~+ (R = H and CH_3): Gas-Phase Catalysis by Argon and Dinitrogen
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Interconversion of ROC~+ and RCO~+ (R = H and CH_3): Gas-Phase Catalysis by Argon and Dinitrogen

机译：ROC〜+和RCO〜+的相互转化（R = H和CH_3）：氩气和双氮气相催化

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摘要

Molecular orbital calculations using density functional theory at the B3LYP/6-311++G(d, p) level have been used to optimize structures for ions COR~+…M and M…RCO~+ and also for the transition structures COR~+…M(ts) for their interconversion (R = H, CH_3 and M = Ar and N_2). For the unsolvated ions and for ions COH~+…M, M HCO~+, and COH~+…M(ts) the optimized structures were used for single-point calculations at QCISD(T)(full)/6-311++G(2df, p). Critical points on the COH~+ and ArCOH~+ potential energy surfaces were also optimized at MP2(full)/6-311++G(3df, 3pd). For the uncomplexed ions COR~+, the barriers to 1, 2-migration of R~+ at B3LYP/6-311++G(d, p) are 35.4 kcal mol~(-1) for R = H and 14.2 kcal mol~(-1) for R = CH_3. Inclusion of a dinitrogen molecule removes this barrier by permitting COR~+ to deposit R~+ on N_2 followed by CO retrieving the R~+ to produce the lower energy isomer, RCO~+. Argon has a lower R~+ affinity than the oxygen atom of CO and does not remove R~+ from COR~+. Preferential stabilization by argon of the transition structure for the 1, 2-migration of R~+ over stabilization of COR~+ at the minimum results in a reduction in the barrier to rearrangement. The gas-phase rearrangements of ions COR~+ via "solvated" transition structures COR~+…Ar(ts) are calculated to have barries of 8.3 kcal mol~(-1) for R = H and 5.7 kcal mol~(-1) for R = CH_3, while for COH~+…Ar at MP2(full)/6-311++G(3df, 3pd) the barrier is only 2.0 kcal mol~(-1). These findings indicate noble gas atoms may catalyze the rearrangement of cations rather than simply cool them by collisions.
机译：使用密度泛函理论在B3LYP / 6-311 ++ G（d，p）水平上的分子轨道计算已用于优化离子COR〜+…M和M…RCO〜+的结构以及过渡结构COR〜 +…M（ts）进行相互转换（R = H，CH_3和M = Ar和N_2）。对于非溶剂化离子和COH〜+…M，M HCO〜+和COH〜+…M（ts）离子，优化结构用于QCISD（T）（full）/ 6-311 +的单点计算+ G（2df，p）。还以MP2（full）/ 6-311 ++ G（3df，3pd）优化了COH〜+和ArCOH〜+势能面上的临界点。对于未络合离子COR〜+，R = +在B3LYP / 6-311 ++ G（d，p）处1〜2迁移的势垒为35.4 kcal mol〜（-1），其中R = H和14.2 kcal对于R ＝ CH_3，mol〜（-1）。通过允许COR〜+将R〜+沉积在N_2上，然后用CO回收R〜+以产生较低能量的异构体RCO〜+，二氮分子的引入消除了该障碍。氩具有比CO的氧原子更低的R〜+亲和力，并且不会从COR〜+中去除R〜+。相对于COR〜+的稳定化，R〜+的1，2迁移的过渡结构通过氩气的优先稳定化导致了重排障碍的减少。计算出通过“溶剂化”过渡结构COR〜+…Ar（ts）对离子COR〜+进行的气相重排，对于R = H和5.7 kcal mol〜（-1），势垒为8.3 kcal mol〜（-1）。 ）对于R = CH_3，而对于MP2（full）/ 6-311 ++ G（3df，3pd）处的COH〜+…Ar，势垒仅为2.0 kcal mol〜（-1）。这些发现表明稀有气体原子可能催化阳离子的重排，而不是简单地通过碰撞使它们冷却。

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