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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Solvent Polarity Tunes the Barrier Height for Twisted Intramolecular Charge Transfer in N-Pyrrolobenzonitrile (PBN)
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Solvent Polarity Tunes the Barrier Height for Twisted Intramolecular Charge Transfer in N-Pyrrolobenzonitrile (PBN)

机译：溶剂极性可调节N-吡咯并苄腈（PBN）中分子内扭曲电荷转移的势垒高度

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摘要

4-(1H-pyrrol-1-yl)benzonitrile (PBN) is a typical intramolecular donor-acceptor (D/A) molecule that shows dual fluorescence in weakly polar environments. In this work the underlying photochemical reaction mechanism is investigated theoretically by using high-level ab initio methods including the recently implemented third order algebraic diagrammatic construction of the polarization propagator (ADC(3)). Solvation effects have been considered by using different sophisticated continuum model approaches. Our results conclusively explain all available experimental findings including the effects of excitation wavelength, temperature and solvent polarity. After photoexcitation in gas phase to the bright 2A (S-2, pi pi*) state, PBN relaxes on the 2A state surface until a conical intersection with the energetically close-lying dark 1B (S1, LE) state is reached. After passing this conical intersection PBN further relaxes on the LE state surface toward a minimum from which emission can occur. In polar environments this picture changes. Then the polar 2B (S3, CT) state is stabilized and an energy barrier along the twisting coordinate vanishes. As a consequence population of the twisted 2B state minimum becomes the dominating decay channel and red-shifted fluorescence occurs.
机译：4-（1H-吡咯-1-基）苄腈（PBN）是典型的分子内供体-受体（D / A）分子，在弱极性环境中显示双重荧光。在这项工作中，通过使用高级从头算方法，包括最近实现的偏振传播器的三阶代数图解结构（ADC（3）），对潜在的光化学反应机理进行了理论研究。已通过使用不同的复杂连续模型方法来考虑了溶剂化作用。我们的结果最终解释了所有可用的实验发现，包括激发波长，温度和溶剂极性的影响。气相光激发至亮2A（S-2，pi pi *）状态后，PBN在2A状态表面上弛豫，直到与能量密集的暗1B（S1，LE）状态形成圆锥形相交。通过此圆锥形相交点后，PBN在LE状态表面上进一步趋于松弛，并朝着最小值发射。在极地环境中，这种情况会发生变化。然后，极性2B（S3，CT）的状态稳定，并且沿扭曲坐标的能垒消失。结果，扭曲的2B态最小值的填充成为主要的衰减通道，并发生红移荧光。

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