Angew. Chem. Int. Edit.: Towards Unveiling the Exact Molecular Structure of Amorphous Red Phosphorus by Single-molecule Studies

Date:2018-12-02Keywords:Red phosphorus, STMView:26

Towards Unveiling the Exact Molecular Structure of Amorphous Red Phosphorus by Single-molecule Studies


Song Zhang,a,+ Hujun Qian,b,+ Zhonghua Liu,c Hongyu Ju,a Zhongyuan Lu,b Haiming Zhang,c Lifeng Chi,c,* Shuxun Cuia,*


a Key Laboratory of Advanced Technologies of Materials (Ministry of Education), Southwest Jiaotong University, Chengdu 610031, China

b State Key Laboratory of Supramolecular Structure and Materials, Institute of Theoretical Chemistry, Jilin University, Changchun 130023, China

c Jiangsu Key Laboratory for Carbon-Based Functional Materials & Devices, Institute of Functional Nano & Soft Materials (FUNSOM), Soochow University, Suzhou, 215123, China


Since the discovery of amorphous red phosphorus (ared P) in 1847, a number of possible structures of a-red P have been proposed. However, the exact molecular structure of a-red P is not determined yet due to the amorphous nature. Here in this study, we utilize several methods to investigate some basic properties of a-red P, which are helpful to determine the structure. The experimental results from scanning tunneling  microscopy (STM) and gel permeation chromatography (GPC) confirm that ared P is a linear inorganic polymer with a broad molecular weight distribution. The theoretical singlemolecule elasticities of the possible ared P structures are obtained by quantum mechanical (QM) calculations. It is found that the experimental singlemolecule elasticity of ared P measured by singlemolecule AFM matches with the theoretical result of the zigzag ladder structure, indicating that ared P may adopt this structure. Although this conclusion needs further validation in the future, this fundamental study represents a helpful attempt to solve the long-lasting riddle of red phosphorus. It is expected that the strategy utilized in this work can be applied to study other inorganic polymers.