A descriptor for the structural stability of organic-inorganic hybrid perovskites based on binding mechanism in electronic structure

Xiaoshuo Liu; Yang Bai; Shengyi Chen; Chongchong Wu; Ian D Gates; Tianfang Huang; Wei Li; Weijie Yang; Zhengyang Gao; Jianxi Yao; Xunlei Ding

doi:10.1007/s00894-022-05046-6

A descriptor for the structural stability of organic-inorganic hybrid perovskites based on binding mechanism in electronic structure

J Mol Model. 2022 Mar 5;28(4):80. doi: 10.1007/s00894-022-05046-6.

Authors

Xiaoshuo Liu^{1

2}, Yang Bai¹, Shengyi Chen¹, Chongchong Wu³, Ian D Gates³, Tianfang Huang², Wei Li^{4

5}, Weijie Yang¹, Zhengyang Gao⁶, Jianxi Yao^{7

8}, Xunlei Ding^{9

10}

Affiliations

¹ Department of Power Engineering, School of Energy, Power, and Mechanical Engineering, North China Electric Power University, Baoding, 071000, China.
² Key Laboratory of Energy Thermal Conversion and Control of Ministry of Education, School of Energy and Environment, Southeast University, Nanjing, 210096, China.
³ Department of Chemical and Petroleum Engineering, University of Calgary, Calgary, AB, T2N 1N4, Canada.
⁴ School of Mathematics and Physics, North China Electric Power University, Beijing, 102206, China.
⁵ Institute of Clusters and Low Dimensional Nanomaterials, School of Mathematics and Physics, North China Electric Power University, Beijing, 102206, China.
⁶ Department of Power Engineering, School of Energy, Power, and Mechanical Engineering, North China Electric Power University, Baoding, 071000, China. gaozhyan@163.com.
⁷ State Key Laboratory of Alternate Electrical Power System With Renewable Energy Sources, North China Electric Power University, Beijing, 102206, China. jianxiyao@ncepu.edu.cn.
⁸ Beijing Key Laboratory of Energy Safety and Clean Utilization, North China Electric Power University, Beijing, 102206, China. jianxiyao@ncepu.edu.cn.
⁹ School of Mathematics and Physics, North China Electric Power University, Beijing, 102206, China. dingxl@ncepu.edu.cn.
¹⁰ Institute of Clusters and Low Dimensional Nanomaterials, School of Mathematics and Physics, North China Electric Power University, Beijing, 102206, China. dingxl@ncepu.edu.cn.

PMID: 35247076
DOI: 10.1007/s00894-022-05046-6

Abstract

The poor stability of organic-inorganic hybrid perovskites hinders its commercial application, which motivates a need for greater theoretical insight into its binding mechanism. To date, the binding mode of organic cation and anion inside organic-inorganic hybrid perovskites is still unclear and even contradictory. Therefore, in this work based on density functional theory (DFT), the binding mechanism between organic cation and anion was systematically investigated through electronic structure analysis including an examination of the electronic localization function (ELF), electron density difference (EDD), reduced density gradient (RDG), and energy decomposition analysis (EDA). The binding strength is mainly determined by Coulomb effect and orbital polarization. Based on the above analysis, a novel 2D linear regression descriptor that E_b = - 9.75Q²/R₀ + 0.00053 V∙E_HL - 6.11 with coefficient of determination R² = 0.88 was proposed to evaluate the binding strength (the units for Q, R₀, V, and E_HL are |e|, Å, bohr³, and eV, respectively), revealing that larger Coulomb effect (Q²/R₀), smaller volume of perovskite (V), and narrower energy difference (E_HL) between the lowest unoccupied molecular orbital (LUMO) of organic cation and the highest occupied molecular orbital (HOMO) of anion correspond to the stronger binding strength, which guides the design of highly stable organic-inorganic hybrid perovskites.

Keywords: Binding energy; Density functional theory; Goldschmidt tolerance factor; Organic–inorganic hybrid perovskites; Structural stability.

Abstract

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