稀有气体基质中水团簇与珊瑚烯相互作用的结构、稳定性和红外光谱

Photochem Pub Date : 2022-03-25 DOI:10.3390/photochem2020018
H. Leboucher, J. Mascetti, Christian Aupetit, J. Noble, A. Simon
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引用次数: 2

摘要

多环芳烃与水的相互作用在大气和天体物理环境中至关重要。我们在这里报道了低温基质中珊瑚烯-水相互作用的理论和实验研究,以及基质对珊瑚烯与水的光活性的影响。该理论研究使用基于混合密度泛函的紧密结合/力场方法来描述捕获在氩基质中的珊瑚烯水团簇,并结合Born-Oppenheimer分子动力学来确定有限温度红外光谱。结合基体分离FTIR光谱实验数据对结果进行了讨论。我们发现,在固相中,(C20H10)(H2O)n的π异构体,n=2或3,在能量上是有利的。这些π配合物的特征是珊瑚烯振动模式的小位移和水带的大位移。这些π结构,在水三聚体的情况下特别稳定,其中水团簇被捕获在珊瑚烯碗中,可能是非平面PAHs与平面PAHs的光活性差异的原因。事实上,嵌入H2O:Ar基质中的平面PAHs,如芘和coronene,在低能紫外线照射下形成σ异构体,并与水反应形成醇和醌,而在相同的实验条件下,未观察到coranolene的光活性。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
Water Clusters in Interaction with Corannulene in a Rare Gas Matrix: Structures, Stability and IR Spectra
The interaction of polycyclic aromatic hydrocarbons (PAHs) with water is of paramount importance in atmospheric and astrophysical contexts. We report here a combined theoretical and experimental study of corannulene-water interactions in low temperature matrices and of the matrix’s influence on the photoreactivity of corannulene with water. The theoretical study was performed using a mixed density functional based tight binding/force field approach to describe the corannulene-water clusters trapped in an argon matrix, together with Born-Oppenheimer molecular dynamics to determine finite-temperature IR spectra. The results are discussed in the light of experimental matrix isolation FTIR spectroscopic data. We show that in the solid phase, π isomers of (C20H10)(H2O)n, with n = 2 or 3, are energetically favored. These π complexes are characterized by small shifts in corannulene vibrational modes and large shifts in water bands. These π structures, particularly stable in the case of the water trimer where the water cluster is trapped “inside” the corannulene bowl, may account for the difference in photoreactivity of non-planar–compared to planar–PAHs with water. Indeed, planar PAHs such as pyrene and coronene embedded in H2O:Ar matrices form σ isomers and react with water to form alcohols and quinones under low energy UV irradiation, whereas no photoreactivity was observed for corannulene under the same experimental conditions.
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CiteScore
3.60
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