Citation: Wang Chen-Guang, Cheng Zhi-Hai, Qiu Xiao-Hui, Ji Wei. Unusually high electron density in an intermolecular non-bonding region: Role of metal substrate[J]. Chinese Chemical Letters, ;2017, 28(4): 759-764. doi: 10.1016/j.cclet.2016.08.004 shu

Unusually high electron density in an intermolecular non-bonding region: Role of metal substrate

a.
Department of Physics and Beijing Key Laboratory of Optoelectronic Functional Materials & Micro-nano Devices, Renmin University of China, Beijing 100872, China
b.
CAS Key Laboratory of Standardization and Measurement for Nanotechnology, CAS Center for Excellence in Nanoscience, National Center for Nanoscience and Technology, Beijing 100190, China

Corresponding author: Cheng Zhi-Hai, chengzh@nanoctr.cn Qiu Xiao-Hui, xhqiu@nanoctr.cn Ji Wei, wji@ruc.edu.cn
Received Date: 31 May 2016
Revised Date: 15 July 2016
Accepted Date: 26 July 2016
Available Online: 3 April 2016

Figures(5)

It has been demonstrated that intermolecular interaction, crucial in a plenty of chemical and physical processes, may vary in the presence of metal surface.However, such modification is yet to be quantitatively revealed.Here, we present a systematical density functional theory study on adsorbed bis(para-pyridyl)acetylene(BPPA)tetramer on Au(111) surface.We observed unusually high electron density between two head-to-head N atoms, an intermolecular "non-bonded" region, in adsorbed BPPA tetramer.This exceptional electron density originates from the wavefunction hybridization of the two compressed N lone-electron-pair states of two BPPA, as squeezed by a newly revealed N-Au-N three-center bonding.This bond, together with the minor contribution from N H-C intermolecular hydrogen bonding, shortens the N-N distance from over 4 Å to 3.30 Å and offers an attractive lateral interacting energy of 0.60 eV, effectively to a surface-confined in-plane pressure.The overlapped non-bonding wavefunction hybridization arising from the effective pressure induced by the N-Au-N three-center bonding, as not been fully recognized in earlier studies, was manifested in non-contact Atomic Force Microscopy.
- Density functional theory,
- Lone electron pairs hybridization,
- N-Au-N three-center bonding,
- In-plane pressure,
- NC-AFM
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