Using Time-Dependent Density Functional Theory to Probe the Nature of Donor-Acceptor Stenhouse Adduct Photochromes
Using Time-Dependent Density Functional Theory to Probe the Nature of Donor-Acceptor Stenhouse Adduct Photochromes
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DOI：
10.1002/cphc.201600041
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发表时间：
2016-06-17
期刊：
影响因子：
2.9
通讯作者：
Jacquemin, Denis
中科院分区：
文献类型：
--
作者：
Laurent, Adele D.;Medved, Miroslav;Jacquemin, Denis
我们提出了最近提出的一类光致变色剂，即供体-受体Stenhouse加合物（DASA）开关的第一个理论研究[J. Am. 2014，136，8169-8172]。通过使用密度泛函理论和它的含时对应物，我们调查的基态和激发态结构，电子跃迁能，和几个属性的两种异构形式。除了证明所选择的理论水平能够再现主要的实验事实之外，我们还证明了：1）DASA光致变色物的两种形式接近于等能; 2）两种异构体具有相似的总偶极矩，尽管它们的尺寸非常不同; 3）两种异构体都具有两性离子性质; 4）在两种形式中，偶极允许的电子激发态的性质是极大不同的;和5）扩展的DASA的特定带形可以通过振动计算再现。
We present the first theoretical investigation of a recently proposed class of photochromes, namely donor-acceptor Stenhouse adduct (DASA) switches [J. Am. Chem. Soc. 2014, 136, 8169-8172]. By using density functional theory and its time-dependent counterpart, we investigate the ground-and excited-state structures, electronic transition energies, and several properties of the two isomeric forms. In addition to demonstrating that the selected level of theory is able to reproduce the main experimental facts, we show that 1) the two forms of the DASA photochromes are close to isoenergetic; 2) the two isomers possess similar total dipole moments, in spite of their very different sizes; 3) both isomers have a zwitterionic nature; 4) the nature of the dipole-allowed electronic excited state is vastly different in the two forms; and 5) the specific band shape of the extended DASA can be reproduced by vibronic calculations.