Toward Quantitative Prediction of Fluorescence Quantum Efficiency by Combining Direct Vibrational Conversion and Surface Crossing: BODIPYs as an Example.,The Journal of Physical Chemistry Letters

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Toward Quantitative Prediction of Fluorescence Quantum Efficiency by Combining Direct Vibrational Conversion and Surface Crossing: BODIPYs as an Example.
The Journal of Physical Chemistry Letters ( IF 4.8 ) Pub Date : 2020-08-07 , DOI: 10.1021/acs.jpclett.0c02054
Qi Ou ₁ , Qian Peng ₂ , Zhigang Shuai ₁

Affiliation

Accurate theoretical description of the electronic structure of boron dipyrromethene (BODIPY) molecules has been a challenge, let alone the prediction of fluorescence quantum efficiency. In this Letter, we show that the electronic structures of BODIPYs can be accurately evaluated via the spin-flip time-dependent density functional theory with the B3LYP functional. With the resulting electronic structures, the experimental spectral line shapes of representative BODIPYs are successfully reproduced by our previously developed thermal vibration correlation function method. Most importantly, a two-channel scheme is proposed to describe the internal conversion of S₁ to S₀ in BODIPYs: channel I via direct vibrational relaxation within the harmonic region and channel II via a distorted S₀/S₁ minimum energy crossing point well away from the harmonic region. The fluorescence quantum yields are accurately predicted within this two-channel scheme, which can therefore serve as a generalized method for predicting the photophysical parameters of organic fluorescent compounds.

中文翻译：

通过直接振动转换和表面交叉相结合对荧光量子效率进行定量预测：以BODIPYs为例。

硼二吡咯亚甲基（BODIPY）分子的电子结构的准确理论描述一直是一个挑战，更不用说荧光量子效率的预测了。在这封信中，我们表明可以通过具有B3LYP功能的自旋翻转时间依赖性密度泛函理论来准确评估BODIPY的电子结构。利用最终的电子结构，通过我们先前开发的热振动相关函数方法成功再现了具有代表性的BODIPY的实验谱线形状。最重要的是，提出了一种两通道方案来描述BODIPY中S ₁到S ₀的内部转换：通道I通过谐波区域内的直接振动弛豫和通道II通过失真的S₀ / S ₁最小能量穿越点远离谐波区域。在此两通道方案中可以准确预测荧光量子产率，因此可以用作预测有机荧光化合物光物理参数的通用方法。

更新日期：2020-09-18

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