Department of Chemistry, Aarhus University, Langelandsgade 140, 8000 Aarhus C, Denmark.
Division of Theoretical Chemistry & Biology, Royal Institute of Technology, Roslagstullsbacken 15, Stockholm, Sweden.
Phys Chem Chem Phys. 2019 Aug 21;21(31):17410-17422. doi: 10.1039/c9cp03039e. Epub 2019 Jul 30.
We report on accurate and efficient calculations of vibrationally resolved emission spectra for oligothiophenes from anharmonic vibrational configuration interaction wave-function calculations in reduced vibrational spaces. These reduced spaces are chosen based on the independent mode displaced harmonic oscillator model. Good agreement with experiment is obtained for all-trans oligothiophenes with two to five rings also when employing only a few active modes. Vibrational modes incorporating inter-ring carbon-carbon stretches and a ring breathing mode are found to be the main players in the vibrational progression for the emission from the first excited electronic state for all investigated oligothiophene derivatives. The presented framework is here illustrated for oligothiophenes, but we have made no underlying system-dependent assumptions and believe it to become a valuable tool for the rational design of fluorescence biomarkers.
我们报告了一种精确高效的方法，通过在缩减的振动空间中进行非谐振动构型相互作用波函数计算，对寡聚噻吩的振动分解发射光谱进行计算。这些缩减空间是基于独立模态位移谐振子模型选择的。对于所有反式具有两个到五个环的寡聚噻吩，即使只使用少数几个活性模态，也可以得到与实验很好的吻合。研究发现，包含环间碳-碳伸缩和环呼吸模式的振动模式是从第一激发电子态发射的振动进展的主要参与者。所提出的框架在这里用寡聚噻吩进行了说明，但我们没有做出任何依赖于系统的假设，并相信它将成为荧光生物标志物合理设计的有用工具。
