论文标题
通过连续辐照度条件连接飞秒的肤色生成量的定量电荷注入电荷模型
A Quantitative Model of Charge Injection by Ruthenium Chromophores Connecting Femtosecond to Continuous Irradiance Conditions
论文作者
论文摘要
Tris(2,2-双吡啶)二苯胺(II)磷酸化和甲基膦式衍生物的超快光体物理学的动力学框架被用作对半导体底物中芳族染料注入电荷的基础。通过包括样品制备过程中光散射,染料扩散和吸附动力学的影响,以及氧化染料的光学响应,可以在跨越纳米环境的时间表的时间表上实现与多个瞬时吸收数据集的定量一致性。特别是,与重要光谱手柄的定量一致性,激发态吸收信号成分与光谱紫外线注入相关的激发态吸收信号成分的衰减以及大约500 nm同胞点的动态红移,验证了我们的动力学模型。在这项工作中估计了电荷注入的伪一阶速率系数,其数量级为1011 S-1至1012 S-1。该模型使极简主义的假设是,特定染料的所有激发态都具有相同的电荷注入系数,该假设将受益于其他理论和实验探索。我们已经调整了该动力学模型以预测连续太阳照射下的电荷注入,并发现每秒每染料每秒多达68个电子转移事件,大大远远超过文献中的先前估计值。
A kinetic framework for the ultrafast photophysics of tris(2,2-bipyridine)ruthenium(II) phosphonated and methyl-phosphonated derivatives is used as a basis for modeling charge injection by ruthenium dyes into a semiconductor substrate. By including the effects of light scattering, dye diffusion and adsorption kinetics during sample preparation, and the optical response of oxidized dyes, quantitative agreement with multiple transient absorption datasets is achieved on timescales spanning femtoseconds to nanoseconds. In particular, quantitative agreement with important spectroscopic handles, decay of an excited state absorption signal component associated with charge injection in the UV region of the spectrum and the dynamical redshift of an approximately 500 nm isosbestic point, validates our kinetic model. Pseudo-first-order rate coefficients for charge injection are estimated in this work, with an order of magnitude ranging 1011 s-1 to 1012 s-1. The model makes the minimalist assumption that all excited states of a particular dye have the same charge injection coefficient, an assumption that would benefit from additional theoretical and experimental exploration. We have adapted this kinetic model to predict charge injection under continuous solar irradiation, and find that as many as 68 electron transfer events per dye per second take place, significantly more than prior estimates in the literature.