Torsional Disorder, Symmetry Breaking, and the Crystal Violet Shoulder Controversy,The Journal of Physical Chemistry Letters

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Torsional Disorder, Symmetry Breaking, and the Crystal Violet Shoulder Controversy
The Journal of Physical Chemistry Letters ( IF 4.8 ) Pub Date : 2023-06-12 , DOI: 10.1021/acs.jpclett.3c01038
Jihad Sissaoui ₁ , Darya S Budkina ₁ , Eric Vauthey ₁

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The nature of the lowest-energy electronic absorption band of crystal violet (CV) and particularly the origin of its high-energy shoulder have been debated since the middle of the past century. The most recent studies invoke a splitting of the S₁ state upon symmetry breaking induced by interactions with the solvent and/or the counterion. Using a combination of stationary and time-resolved polarized spectroscopy together with quantum-chemical calculations, we show that torsional disorder in the ground-state results in an inhomogeneous broadening of the absorption band of CV. The center of the band is mostly due to symmetric molecules with a degenerate S₁ state, whereas the edges originate from transitions to the S₁ and S₂ states of distorted symmetry-broken molecules. Transient-absorption measurements with different excitation wavelengths reveal that these two groups of molecules interconvert rapidly in liquid but not in a rigid environment.

中文翻译：

扭转失调、对称性破缺和水晶紫肩争议

自上世纪中叶以来，结晶紫（CV）最低能量电子吸收带的性质，特别是其高能肩的起源一直存在争议。最近的研究在与溶剂和/或抗衡离子的相互作用引起对称性破缺时引发了 S _{1态的分裂。}通过结合静态偏振光谱和时间分辨偏振光谱以及量子化学计算，我们发现基态扭转无序会导致 CV 吸收带不均匀展宽。带的中心主要是由于具有简并 S ₁态的对称分子，而边缘源自向 S ₁和 S _2的跃迁扭曲的对称性破缺分子的状态。使用不同激发波长的瞬态吸收测量表明，这两组分子在液体中快速相互转化，但在刚性环境中则不然。

更新日期：2023-06-12

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