Kekulene: Structure, stability and nature of H•••H interactions in large PAHs

Q2 Physics and Astronomy

Molecular Astrophysics Pub Date : 2017-09-01 DOI:10.1016/j.molap.2017.05.003

J. Poater , J. Paauwe , S. Pan , G. Merino , C. Fonseca Guerra , F.M. Bickelhaupt

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引用次数: 13

Abstract

We have quantum chemically analyzed how the stability of small and larger polycyclic aromatic hydrocarbons (PAHs) is determined by characteristic patterns in their structure using density functional theory at the BLYP/TZ2P level. In particular, we focus on the effect of the nonbonded H•••H interactions that occur in the bay region of kinked (or armchair) PAHs, but not in straight (or zigzag) PAHs. Model systems comprise anthracene, phenanthrene, and kekulene as well as derivatives thereof. Our main goals are: (1) to explore how nonbonded H•••H interactions in armchair configurations of kinked PAHs affect the geometry and stability of PAHs and how their effect changes as the number of such interactions in a PAH increases; (2) to understand the extent of stabilization upon the substitution of a bay CH fragment by either C^• or N; and (3) to examine the origin of such stabilizing/destabilizing interactions.

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Kekulene:大PAHs中H•••H相互作用的结构、稳定性和性质

我们利用BLYP/TZ2P水平的密度泛函理论，用量子化学方法分析了大小多环芳烃(PAHs)的稳定性是如何由其结构的特征模式决定的。特别地，我们关注的是非键的H•••H相互作用的影响，这种相互作用发生在扭结(或扶手椅)多环芳烃的海湾区域，而不是在直(或之字形)多环芳烃中。模型系统包括蒽、菲和蒽及其衍生物。我们的主要目标是:(1)探索扭结多环芳烃扶手椅构型中的非键H•••H相互作用如何影响多环芳烃的几何形状和稳定性，以及它们的影响如何随着这种相互作用数量的增加而变化;(2)了解C•或N取代海湾CH片段后的稳定程度;(3)研究这种稳定/不稳定相互作用的起源。

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来源期刊

Molecular Astrophysics ASTRONOMY & ASTROPHYSICS-

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期刊介绍： Molecular Astrophysics is a peer-reviewed journal containing full research articles, selected review articles, and thematic issues. Molecular Astrophysics is a new journal where researchers working in planetary and exoplanetary science, astrochemistry, astrobiology, spectroscopy, physical chemistry and chemical physics can meet and exchange their ideas. Understanding the origin and evolution of interstellar and circumstellar molecules is key to understanding the Universe around us and our place in it and has become a fundamental goal of modern astrophysics. Molecular Astrophysics aims to provide a platform for scientists studying the chemical processes that form and dissociate molecules, and control chemical abundances in the universe, particularly in Solar System objects including planets, moons, and comets, in the atmospheres of exoplanets, as well as in regions of star and planet formation in the interstellar medium of galaxies. Observational studies of the molecular universe are driven by a range of new space missions and large-scale scale observatories opening up. With the Spitzer Space Telescope, the Herschel Space Observatory, the Atacama Large Millimeter/submillimeter Array (ALMA), NASA''s Kepler mission, the Rosetta mission, and more major future facilities such as NASA''s James Webb Space Telescope and various missions to Mars, the journal taps into the expected new insights and the need to bring the various communities together on one platform. The journal aims to cover observational, laboratory as well as computational results in the galactic, extragalactic and intergalactic areas of our universe.