High-Throughput Pressure-Dependent Density Functional Theory Investigation of Herringbone Polycyclic Aromatic Hydrocarbons: Part 1. Pressure-Dependent Structure Trends
High-Throughput Pressure-Dependent Density Functional Theory Investigation of Herringbone Polycyclic Aromatic Hydrocarbons: Part 1. Pressure-Dependent Structure Trends
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DOI：
10.1021/acs.jpcc.8b07209
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发表时间：
2018-09
期刊：
影响因子：
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通讯作者：
M. Hammouri;Taylor M. Garcia;C. Cook;Stephen Monaco;S. Jezowski;N. Marom;Bohdan Schatschneider
中科院分区：
文献类型：
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作者：
M. Hammouri;Taylor M. Garcia;C. Cook;Stephen Monaco;S. Jezowski;N. Marom;Bohdan Schatschneider
摘要：已知外部压力会改变软材料的分子和结构构象，导致分子间相互作用以及固有物理性质的变化。在两部分研究的第一部分中，我们引入压力在色散包含密度泛函理论框架（DFT+vdW）内扰动40个结晶的人字形多环芳烃（HB-PAH）的结构和分子间相互作用。所施加的压力导致晶体晶胞、分子间相互作用和分子构象的改变。通常，晶胞长度/体积随着压力的增加而单调减小。Hirshfeld表面分析表明，随着压力的增加，C●H和C ● C分子间紧密接触分数增加，H ● H相互作用减少。C●H和C ●C分子间相互作用的增加增强了C-H● π和π ● π相互作用，降低了分子间的相互作用。
Abstract: External pressure is known to alter the molecular and structural conformations of soft materials, leading to changes in the intermolecular interactions as well as the inherent physical properties. In part 1 of a two-part investigation, we introduce pressure within the dispersion-inclusive density functional theory framework (DFT+vdW) to perturb the structures and intermolecular interactions of 40 crystalline, herringbone polycyclic aromatic hydrocarbons (HB-PAHs). The applied pressure results in alterations of the crystalline unit cells, intermolecular interactions, and molecular conformations. In general, the unit cell lengths/volumes decrease monotonously with increasing pressure. Hirshfeld surface analysis typically reveals an increase in the C●●●H and C●●●C intermolecular close contact fractions with increased pressure, and a decrease in the H●●●H interactions. The increase in the C●●●H and C●●●C intermolecular interactions enhances the C-H●●●π and π●●●π interactions, decreasing intermolecul...