Interplay between TiO2 Surfaces and Organic Photochromes: A DFT Study of Adsorbed Azobenzenes and Diarylethenes
Interplay between TiO2 Surfaces and Organic Photochromes: A DFT Study of Adsorbed Azobenzenes and Diarylethenes
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DOI：
10.1021/jp510535p
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发表时间：
2015-02-19
影响因子：
3.7
通讯作者：
Jacquemin, Denis
中科院分区：
文献类型：
--
作者：
Chen, Kathy J.;Charaf-Eddin, Azzam;Jacquemin, Denis
由于光致变色剂作为光诱导的分子开关，有相当大的兴趣在输出其分子功能在固态，以开发光响应材料。在此背景下，我们进行了DFT研究的一系列的光致变色衍生物的反/顺-偶氮苯和开放/封闭的二芳基乙烯吸附在金红石（110）和金红石（101）板。通过改变助色和光致变色状态，我们研究了表面吸附物相互作用的电子结构，吸附几何形状，和贝德电荷转移的趋势。使用主成分分析，我们演示了如何孤立的光致变色的方向上的锚定基团的偶极矩是最重要的预测吸附系统的电子结构。本文的一个关键点是显示如何孤立的光致变色和裸板的能级变化作为吸附的结果，以及如何第一性原理建模有助于合理化和预测这些趋势。
Because photochromes act as light-induced molecular switches, there is considerable interest in exporting their molecular functionality in the solid state in order to develop photoresponsive materials. In that context, we have carried out a DFT investigation of a series of photochromic derivatives of trans/cis-azobenzene and open/closed-diarylethene adsorbed onto rutile (110) and anatase (101) slabs. By varying the auxochromes and the photochromic state, we examine the trends in the surface-adsorbate interplay in terms of the electronic structure, adsorption geometries, and Bader charge transfer. Using principal components analysis, we demonstrate how the dipole moment of the isolated photochrome in the direction of the anchoring group is the most important predictor of the electronic structure of the adsorbed system. A key point of this paper is to show how the energy levels of the isolated photochrome and bare slab change as a result of adsorption and how first-principles modeling helps to rationalize and predict these trends.