Understanding the adsorption of CuPc and ZnPc on noble metal surfaces by combining quantum-mechanical modelling and photoelectron spectroscopy.
Understanding the adsorption of CuPc and ZnPc on noble metal surfaces by combining quantum-mechanical modelling and photoelectron spectroscopy.
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DOI：
10.3390/molecules19032969
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发表时间：
2014-03-07
期刊：
影响因子：
--
通讯作者：
Zojer E
中科院分区：
文献类型：
--
作者：
Huang YL;Wruss E;Egger DA;Kera S;Ueno N;Saidi WA;Bucko T;Wee AT;Zojer E
酞菁是一类重要的有机半导体，因此，它们与金属的界面既具有基础性又具有实际意义。在目前的贡献，我们提供了一个相结合的理论和实验研究，在其中，我们表明，国家的最先进的量子力学模拟是现在能够处理这种接口的大多数属性在定量可靠的方式。这对于在Au（111）和Ag（111）表面上的Cu-酞菁（CuPc）和Zn-酞菁（ZnPc）示出。使用最近开发的方法，有效地处理货车德瓦耳斯（VDW）在金属/有机界面的相互作用，我们计算吸附几何形状与实验非常吻合。有了这些几何形状，我们就能够准确地描述分子吸附所产生的界面电子结构。我们发现，键合占主导地位的VDW力的所有研究接口。同时，Au（111）上的电荷重排完全是由于泡利推回。在Ag（111）上，我们还观察到电荷从金属转移到与分子最低未占π态相关的自旋通道之一。比较界面态密度与我们的紫外光电子能谱（UPS）实验，我们发现，使用一个混合泛函是必要的，以获得正确的电子态的顺序。
Phthalocyanines are an important class of organic semiconductors and, thus, their interfaces with metals are both of fundamental and practical relevance. In the present contribution we provide a combined theoretical and experimental study, in which we show that state-of-the-art quantum-mechanical simulations are nowadays capable of treating most properties of such interfaces in a quantitatively reliable manner. This is shown for Cu-phthalocyanine (CuPc) and Zn-phthalocyanine (ZnPc) on Au(111) and Ag(111) surfaces. Using a recently developed approach for efficiently treating van der Waals (vdW) interactions at metal/organic interfaces, we calculate adsorption geometries in excellent agreement with experiments. With these geometries available, we are then able to accurately describe the interfacial electronic structure arising from molecular adsorption. We find that bonding is dominated by vdW forces for all studied interfaces. Concomitantly, charge rearrangements on Au(111) are exclusively due to Pauli pushback. On Ag(111), we additionally observe charge transfer from the metal to one of the spin-channels associated with the lowest unoccupied π-states of the molecules. Comparing the interfacial density of states with our ultraviolet photoelectron spectroscopy (UPS) experiments, we find that the use of a hybrid functionals is necessary to obtain the correct order of the electronic states.
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影响因子：
3
作者：
Grimme, Stefan
通讯作者：
Grimme, Stefan
影响因子：
3.7
作者：
Egger, David A.;Ruiz, Victor G.;Said, Wissam A.;Bucko, Tomas;Tkatchenko, Alexandre;Zojer, Egbert
通讯作者：
Zojer, Egbert
影响因子：
4.4
作者：
Biller, Ariel;Tamblyn, Isaac;Kronik, Leeor
通讯作者：
Kronik, Leeor
影响因子：
3.7
作者：
Garcia-Lastra, J. M.;Rostgaard, C.;Thygesen, K. S.
通讯作者：
Thygesen, K. S.
影响因子：
3.8
作者：
CSASZAR, P;PULAY, P
通讯作者：
PULAY, P