Adsorption of Terarylenes on Ag(111) and NaCl(001)/Ag(111): A Scanning Tunneling Microscopy and Density Functional Theory Study
Adsorption of Terarylenes on Ag(111) and NaCl(001)/Ag(111): A Scanning Tunneling Microscopy and Density Functional Theory Study
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四芳撑在 Ag(111) 和 NaCl(001)/Ag(111) 上的吸附：扫描隧道显微镜和密度泛函理论研究
DOI：
10.1021/acs.jpcc.7b11122
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发表时间：
2018
期刊：
影响因子：
--
通讯作者：
Kawai Tsuyoshi
中科院分区：
文献类型：
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作者：
Calupitan Jan Patrick Dela Cruz;Guillermet Olivier;Galangau Olivier;Yengui Mayssa;Echeverria Jorge;Bouju Xavier;Nakashima Takuya;Rapenne Gwenael ;Coratger Roland;Kawai Tsuyoshi
光开关材料是下一代光电子器件的构建块，其可能需要在固体基底上沉积分子。然而，由于表面与分子的相互作用和对称性考虑，分子性质在吸附后发生变化。扫描隧道显微镜（STM）和密度泛函理论（DFT）提供的技术，以解决功能分子的相互作用下降到单分子水平上的固体基板。本文采用扫描隧道显微镜（STM）和密度泛函理论（DFT）相结合的方法，研究了Ag（111）和NaCl（001）/Ag（111）表面上的叔丁基功能化的Terarylene分子在0.5 K时的三种构象。DFT计算表明，其中两种构象是指在气相中的反式构象的不同吸附几何。另一个被分配到nonreactivecisconformation。这是第一次，这种构象被分离和成像在单分子水平。计算进一步表明，除了分子的电子结构之外，表面突出的甲基是STM上观察到的亮点的起源。在NaCl（001）/Ag（111）上，首次发现了反式构象，并首次完成了四芳烯的占据态和未占据态的作图。
Photoswitching materials are building blocks of next generation optoelectronic devices which may require molecule deposition on a solid substrate. However, molecule properties change upon adsorption due to surface-molecule interactions and symmetry considerations. Scanning tunneling microscopy (STM) and density functional theory (DFT) offer techniques to address interactions of functional molecules down to the single-molecular level on solid substrates. In this paper, we present a combined STM and DFT study of atert-butyl functionalized terarylene molecule on Ag(111) and NaCl(001)/Ag(111) at ∼5 K.tert-Butyl groups aided in identifying three conformations of the compound upon adsorption on the surface. DFT calculations showed that two of these conformations refer to different adsorption geometries of thetransconformation in the gas phase. The other was assigned to the nonreactivecisconformation. For the first time, this conformation was isolated and imaged at the single-molecular level. Calculations further showed that aside from the electronic structure of the molecule, methyl groups sticking out of the surface are the origin of bright spots observed on the STM. On NaCl(001)/Ag(111), only thetransconformation was found and the mapping of occupied and unoccupied states of terarylenes was accomplished for the first time.