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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Absolute Binding Energies of Alkali-Metal Cation Complexes with Benzene Determined by Threshold Collision-Induced Dissociation Experiments and ab Initio Theory
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Absolute Binding Energies of Alkali-Metal Cation Complexes with Benzene Determined by Threshold Collision-Induced Dissociation Experiments and ab Initio Theory

机译：阈值碰撞诱导解离实验和从头算理论确定的碱金属阳离子配合物与苯的绝对结合能

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摘要

The sequential bond dissociation energies (BDEs) of the mono- and bis-benzene complexes with alkali metal cations (Li+, Na+, K+, Rb+, and Cs+) are determined experimentally by collision-induced dissociation (CID) with Xe in a guided ion beam mass spectrometer and theoretically by ab initio calculations. The kinetic energy dependence of the cm cross sections are analyzed to yield O and 298 K bond energies for (C6H6)x-IM+- C6~ (x = 1-2) after accounting for the effects of the internal energies of the reactant ions, the multiple collisions of the ions with xenon, and the dissociation lifetimes of the ionic complexes. Ab initio binding energies are calculated at the MP2(full)/6-311 +G(2d,2p)//MP2(full)/6-3l G* level and corrected for zero- point energies (ZPE) and basis set superposition errors (ESSE). The theoretical EDEs are in reasonably good agreement with the experimentally determined O K bond energies when full electron correlation is included (for Li+ , Na+ , and K+) but differ appreciably when effective core potentials (ECPs) are used for the K+ , Rb+, and Cs+ metal ions. The trends in M+(C~6)x binding energies are explained in terms of varying magnitudes of electrostatic interactions and ligand-Iigand repulsions in the complexes. Agreement between our BDEs and the few previous experimental M+(C6H6)x EDEs is found to be good in most cases. Comparisons are also made to previous theoretical M+(~)% EDEs in the literature and to the experimental EDEs of alkali-metal ion-water and alkali-metal ion-dimethyl ether complexes.
机译：单和双苯配合物与碱金属阳离子（Li +，Na +，K +，Rb +和Cs +）的顺序键解离能（BDE）是通过在导向离子中与Xe的碰撞诱导解离（CID）实验确定的束质谱仪和理论上由头算计算。考虑到反应物离子的内部能量的影响，分析了cm截面的动能依赖性，得出了（C6H6）x-IM +-C6〜（x = 1-2）的O和298 K键能，离子与氙的多次碰撞以及离子配合物的离解寿命。从头计算结合能以MP2（满）/ 6-311 + G（2d，2p）// MP2（满）/ 6-3l G *水平计算，并针对零点能量（ZPE）和基集叠加进行校正错误（ESSE）。当包括全电子相关性（对于Li +，Na +和K +）时，理论EDE与实验确定的OK键能具有相当好的一致性，但是当对K +，Rb +和Cs +使用有效核心电势（ECP）时，理论上的EDE明显不同金属离子。 M +（C〜6）x结合能的趋势是根据复合物中静电相互作用和配体-配体排斥的变化幅度来解释的。在大多数情况下，我们的BDE与先前的少数实验M +（C6H6）x EDE之间的一致性被认为是很好的。还与文献中先前的理论M +（〜）％EDE以及碱金属离子-水和碱金属离子-二甲醚络合物的实验EDE进行了比较。

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