Theoretical Analysis of the Intermolecular Interaction Effects on the Excitation Energy of Organic Pigments: Solid State Quinacridone
Theoretical Analysis of the Intermolecular Interaction Effects on the Excitation Energy of Organic Pigments: Solid State Quinacridone
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DOI：
10.1021/jp804943m
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发表时间：
2008-10-30
影响因子：
2.9
通讯作者：
Kitaura, Kazuo
中科院分区：
文献类型：
--
作者：
Fukunaga, Hiroo;Fedorov, Dmitri G.;Kitaura, Kazuo
喹吖啶酮(QAS)是一种有机氢键颜料，根据其晶体结构的不同，在溶液中呈黄色，在固相中呈红色至紫色。我们对QA的α(1)晶相、β晶相和伽马晶相进行了基于规则和碎片分子轨道的含时密度泛函理论(TDDFT)计算，以考察固相光谱漂移的原因。在TDDFIF计算的基础上，我们发现QA的光谱从气相到固相的移动是由结构形变、静电势(晶场)和分子间相互作用的相互作用决定的，并且每个贡献都是相同数量级的。结构形变引起的光谱位移主要是由C=O键的伸展引起的。分子间的相互作用对基色和亚色位移的贡献取决于空间取向，它们的总和导致基色位移。
Quinacridones (QAs) are organic hydrogen-bonded pigments, which are yellow in solution and become reddish to violet in solid phase depending on the crystal structure. We have carried out regular and fragment molecular orbital (FMO) based time-dependent density functional theory (TDDFT) calculations of the alpha(1), beta, and gamma crystalline phases of QA to examine the origin of the spectral shift in the solid phase. On the basis of the TDDFIF calculations, we have found that the spectral shift from gas to solid phase in QA is dominated by the interplay of the structural deformation, electrostatic potential (crystal field), and intermolecular interactions, and each contribution is of the same order of magnitude. The spectral shift induced by the structural deformation is mainly caused by the stretch of the C=O bond. The individual intermolecular interactions contribute to bathochromic and hypsochromic shifts depending on the spatial orientation, and their sums result in the bathochromic shift overall.