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首页> 外文期刊>Chemistry: A European journal >Binding Energies of the pi-Stacked Anisole Dimer: New Molecular Beam-Laser Spectroscopy Experiments and CCSD(T) Calculations
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Binding Energies of the pi-Stacked Anisole Dimer: New Molecular Beam-Laser Spectroscopy Experiments and CCSD(T) Calculations

机译：π堆积茴香醚二聚体的结合能：新的分子束激光光谱实验和CCSD（T）计算

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摘要

Among noncovalent interactions, pi-pi stacking is a very important binding motif governed mainly by London dispersion. Despite its importance, for instance, for the structure of bio-macromolecules, the direct experimental measurement of binding energies in pi-pi stacked complexes has been elusive for a long time. Only recently, an experimental value for the binding energy of the anisole dimer was presented, determined by velocity mapping ion imaging in a two-photon resonant ionisation molecular beam experiment. However, in that paper, a discrepancy was already noted between the obtained experimental value and a theoretical estimate. Here, we present an accurate recalculation of the binding energy based on the combination of the CCSD(T)/CBS interaction energy and a DFT-D3 vibrational analysis. This proves unambiguously that the previously reported experimental value is too high and a new series of measurements with a different, more sensitive apparatus was performed. The new experimental value of 1800 +/- 100 cm(-1) (5.15 +/- 0.29 kcal mol(-1)) is close to the present theoretical prediction of 5.04 +/- 0.40 kcal mol(-1). Additional calculations of the properties of the cationic and excited states involved in the photodissociation of the dimer were used to identify and rationalise the difficulties encountered in the experimental work.
机译：在非共价相互作用中，pi-pi堆积是一个非常重要的结合基序，主要受伦敦分散的支配。例如，尽管对于生物大分子的结构非常重要，但是直接实验测量pi-pi堆积复合物中结合能的方法却一直遥不可及。直到最近，才提出了苯甲醚二聚体结合能的实验值，该值是通过在两个光子共振电离分子束实验中通过速度映射离子成像确定的。但是，在该论文中，已经注意到了获得的实验值与理论估计之间的差异。在这里，我们基于CCSD（T）/ CBS相互作用能和DFT-D3振动分析的结合，给出了结合能的精确重新计算。这清楚地证明了先前报告的实验值过高，并且使用了另一种更灵敏的仪器进行了一系列新的测量。新的实验值1800 +/- 100 cm（-1）（5.15 +/- 0.29 kcal mol（-1））接近目前的理论预测值5.04 +/- 0.40 kcal mol（-1）。涉及二聚体光解离的阳离子和激发态性质的其他计算可用于识别和合理化实验工作中遇到的困难。

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