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Unraveling substituent effects on frontier orbitals of conjugated molecules using an absolutely localized molecular orbital based analysis

机译：使用基于绝对局部分子轨道的分析揭示取代基对共轭分子前沿轨道的影响

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摘要

It is common to introduce electron-donating or electron-withdrawing substituent groups into functional conjugated molecules (such as dyes) to tune their electronic structure properties (such as frontier orbital energy levels) and photophysical properties (such as absorption and emission wavelengths). However, there lacks a generally applicable tool that can unravel the underlying interactions between orbitals from a substrate molecule and those from its substituents in modern electronic structure calculations, despite the long history of qualitative molecular orbital theory. In this work, the absolutely localized molecular orbitals (ALMO) based analysis is extended to analyze the effects of substituent groups on the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) of a given system. This provides a bottom-up avenue towards quantification of effects from distinct physical origins (e.g. permanent electrostatics/Pauli repulsion, mutual polarization, inter-fragment orbital mixing). For the example case of prodan (a typical dye molecule), it is found that inter-fragment orbital mixing plays a key role in narrowing the HOMO–LUMO gap of the naphthalene core. Specifically, an out-of-phase mixing of high-lying occupied orbitals on the naphthalene core and the dimethylamino group leads to an elevated HOMO, whereas an in-phase combination of LUMOs on the naphthalene core and the propionyl group lowers the LUMO energy of the entire molecule. We expect this ALMO-based analysis to bridge the gap between concepts from qualitative orbital interaction analysis and quantitative electronic structure calculations.
机译：通常将给电子或吸电子取代基引入功能共轭分子（例如染料）中，以调节其电子结构性质（例如前沿轨道能级）和光物理性质（例如吸收和发射波长）。然而，尽管定性分子轨道理论由来已久，但在现代电子结构计算中，仍缺乏一种通用的工具来揭示底物分子的轨道与其取代基的轨道之间的潜在相互作用。在这项工作中，基于绝对局部分子轨道（ALMO）的分析被扩展为分析取代基对给定系统的最高占据分子轨道（HOMO）和最低未占据分子轨道（LUMO）的影响。这提供了一种从下至上的途径，可用于量化来自不同物理起源（例如永久静电/保利排斥，相互极化，碎片间的轨道混合）的效应。以prodan（典型的染料分子）为例，发现片段间的轨道混合在缩小萘核的HOMO-LUMO间隙中起关键作用。具体而言，萘核上高位占据的轨道与二甲氨基的异相混合会导致HOMO升高，而萘核上的LUMO与丙酰基的同相结合会降低LUMO能量。整个分子。我们希望基于ALMO的分析能够弥合定性轨道相互作用分析和定量电子结构计算之间的概念鸿沟。

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