Theoretical investigation of the mechanism and dynamics of intramolecular coherent resonance energy transfer in soft molecules: a case study of dithia-anthracenophane.
Theoretical investigation of the mechanism and dynamics of intramolecular coherent resonance energy transfer in soft molecules: a case study of dithia-anthracenophane.
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软分子分子内相干共振能量转移机制和动力学的理论研究：以二硫蒽芬为例。
DOI：
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发表时间：
2010
影响因子：
15
通讯作者：
Seogjoo J. Jang
中科院分区：
文献类型：
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作者：
Lei Yang;S. Caprasecca;B. Mennucci;Seogjoo J. Jang
对双硫杂菲(DTA)和二甲基菲(DMA)进行了计算研究，DTA中存在相干共振能量传递动力学的实验证据，二甲基菲是DTA中代表能量供体和受体的分子。用组态相互作用单分子(CIS)和含时密度泛函理论(TD-DFT)方法计算了电子激发能，并与实验值进行了比较。采用基于跃迁密度的方法计算了嵌入到DTA基态结构中的两个DMA之间的电子耦合常数。与基于DTA激发能的一半能级间距的实验结果相比，电子耦合的结果提供了更一致的实验解释。基于可极化连续介质模型(PCM)研究了溶剂化效应。溶剂激发极化和屏蔽效应的贡献是相反的，净电子耦合与真空中的值差别不大。根据最近发展的相干共振能量转移理论，对相干布居转移的可能性进行了评估。结果表明，BaS的时间尺度对维持量子相干性有重要作用。量子化学和动力学数据的结合表明，差热分析中的电子耦合在50-100 cm(-1)范围内。振荡激发布居动力学的存在可以从极化子激发适度地包裹着色散振动模的图像中得到理解。在扭转角约束的优化结构基础上，研究了扭转调制对差热分析和电子耦合激发能的影响。结果表明，在差热分析中不能忽略扭转运动引起的非弹性效应。
A computational study is conducted on dithia-anthracenophane (DTA), for which there is experimental evidence for coherent resonance energy transfer dynamics, and on dimethylanthracene (DMA), a molecule representing the energy donor and the acceptor in DTA. Electronic excitation energies are calculated by configuration interaction singles (CIS) and time-dependent density functional theory (TD-DFT) methods and are compared to experimental ones. Electronic coupling constants are calculated between two DMAs embedded into the ground-state structure of DTA employing methods based on transition densities. The resulting values of electronic coupling provide a more consistent interpretation of experiments than those based on one-half the level spacing of DTA excitation energies. Solvation effects are studied based on the polarizable continuum model (PCM). Solvent-induced polarization and screening effects are shown to make opposite contributions, and the net electronic coupling is little different from the value in a vacuum. The likelihood of coherent population transfer is assessed on the basis of a recently developed theory of coherent resonance energy transfer. The time scale of bath is shown to have an important role in sustaining the quantum coherence. The combination of quantum chemical and dynamical data suggests that the electronic coupling in DTA is in the range of 50-100 cm(-1). The presence of oscillatory excitation population dynamics can be understood from the picture of polaronic excitation moderately dressed with dispersive vibrational modes. The effect of torsional modulation on the excitation energies of DTA and electronic coupling is examined on the basis of optimized structures with the torsional angle constrained. The result suggests that inelastic effect due to torsional motion cannot be disregarded in DTA.
影响因子：
15
作者：
Liu, Wenhao;Greytak, Andrew B.;Lee, Jungmin;Wong, Cliff R.;Park, Jongnam;Marshall, Lisa F.;Jiang, Wen;Curtin, Peter N.;Ting, Alice Y.;Nocera, Daniel G.;Fukumura, Dai;Jain, Rakesh K.;Bawendi, Moungi G.
通讯作者：
Bawendi, Moungi G.