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金属配合物[Mg(CH₃OH)ₙ](²⁺)、[Ca(CH₃OH)ₙ](²⁺)和[Sr(CH₃OH)ₙ](²⁺)(n取值范围为4至20)的实验结合能

Experimental binding energies for the metal complexes [Mg(CH3OH)n](2+), [Ca(CH3OH)n](2+), and [Sr(CH3OH)n](2+) for n in the range 4-20.

作者信息

Bruzzi E, Stace A J

机构信息

Department of Physical and Theoretical Chemistry, School of Chemistry, University of Nottingham , University Park, Nottingham NG7 2RD, United Kingdom.

出版信息

J Phys Chem A. 2014 Oct 9;118(40):9357-63. doi: 10.1021/jp508131h. Epub 2014 Sep 24.

DOI:10.1021/jp508131h
PMID:25231925
Abstract

A supersonic source of clusters has been used to prepare neutral complexes of methanol in association with an alkaline earth metal atom. From these complexes the following metal-containing dications have been generated through electron ionization: Mg(CH3OH)n, Ca(CH3OH)n, and Sr(CH3OH)n, and for n in the range 4-20, kinetic energy release measurements following the evaporation of a single molecule have been undertaken using a high resolution mass spectrometer. Using finite heat bath theory, these data have been transformed into binding energies for individual methanol molecules attached to each of the three cluster systems. In the larger complexes (n > 6) the results exhibit a consistent trend, whereby the experimental binding energy data for all three metal ions are similar, suggesting that the magnitude of the charge rather than charge density influences the strength of the interaction. From a comparison with data recorded previously for (CH3OH)nH(+) it is found that the 2+ charge on a metal ion has an effect on the binding energy of molecules in complexes containing up to 20 solvent molecules. The results recorded for Ca(CH3OH)n show evidence of a very marked transition between n = 6 and 7, which is thought to coincide with the completion of a primary solvation shell and the onset of molecules starting to occupy a second and most probably a third shell.

摘要

一个超音速团簇源已被用于制备甲醇与碱土金属原子结合的中性配合物。通过电子电离从这些配合物中产生了以下含金属的二价阳离子:Mg(CH₃OH)ₙ、Ca(CH₃OH)ₙ和Sr(CH₃OH)ₙ,对于n在4至20范围内,使用高分辨率质谱仪对单个分子蒸发后的动能释放进行了测量。利用有限热浴理论,这些数据已被转换为附着在这三个团簇体系中每个体系上的单个甲醇分子的结合能。在较大的配合物(n > 6)中,结果呈现出一致的趋势,即所有三种金属离子的实验结合能数据相似,这表明电荷的大小而非电荷密度影响相互作用的强度。通过与先前记录的(CH₃OH)ₙH(⁺)的数据进行比较发现,金属离子上的2+电荷对含有多达20个溶剂分子的配合物中分子的结合能有影响。Ca(CH₃OH)ₙ记录的结果显示在n = 6和7之间有一个非常明显的转变迹象,这被认为与第一溶剂化壳层的完成以及分子开始占据第二且很可能是第三壳层的开始相吻合。

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