Introducing hafnium to atomically small- and medium-sized tin clusters (HfSnn0/-/2- (n = 4-17)): A computational investigation of geometrical and growth behavior, spectral properties, electronic configuration and thermochemistry

Yanpeng Zhang; Jucai Yang; Caixia Dong; Xiaojun Li

doi:10.1016/j.saa.2024.124277

Introducing hafnium to atomically small- and medium-sized tin clusters (HfSn_n^0/-/2- (n = 4-17)): A computational investigation of geometrical and growth behavior, spectral properties, electronic configuration and thermochemistry

Spectrochim Acta A Mol Biomol Spectrosc. 2024 Jul 5:315:124277. doi: 10.1016/j.saa.2024.124277. Epub 2024 Apr 13.

Authors

Yanpeng Zhang¹, Jucai Yang², Caixia Dong³, Xiaojun Li⁴

Affiliations

¹ College of Chemical Engineering, Inner Mongolia University of Technology, and Inner Mongolia Key Laboratory of Theoretical and Computational Chemistry Simulation, Hohhot 010051, People's Republic of China.
² College of Chemical Engineering, Inner Mongolia University of Technology, and Inner Mongolia Key Laboratory of Theoretical and Computational Chemistry Simulation, Hohhot 010051, People's Republic of China; College of Resources and Environmental Engineering, Inner Mongolia University of Technology, Hohhot 010051, People's Republic of China.
³ College of Resources and Environmental Engineering, Inner Mongolia University of Technology, Hohhot 010051, People's Republic of China. Electronic address: dongcx@imut.edu.cn.
⁴ College of Science, Xi'an University of Posts and Telecommunications, Xi'an 710121, Shaanxi, People's Republic of China. Electronic address: xjli@xupt.edu.cn.

PMID: 38636426
DOI: 10.1016/j.saa.2024.124277

Abstract

The global and local minimum configurations of single Hf atom doped Sn clusters are conducted via density function theory (DFT) combined with artificial bee colony algorithm (ABCluster). Furthermore, DFT method is also used to systematically investigate on their structural growth evolution, spectral and electronic information, thermochemical properties following the size of tin clusters doped Hf atom. Structurally, the ground-state geometries of neutral, anion and di-anion are discovered that, from n = 4, the number of Sn atoms in cluster, HfSn_n^0/-^/2- adsorb additional Sn atom on the prior architecture one by one until forming n = 17 for HfSn_n_-1^0/-, as well as forming n = 16 for HfSn_n_-1^2-. And for the HfSn₁₁^0/- and HfSn₁₀^2- as beginning the species veritably develop sealed architectures. The strongest vibrational modes of sealed nanoclusters are stretching modes of Hf atom with infrared actives and breathing modes of the Sn cage framework with Raman actives, respectively. The natural population analysis (NPA) elucidates the stronger relationship between the Hf atoms and the tin frameworks in sealed clusters than that in unsealed clusters. The results of thermochemical properties, molecular orbital shell (MOs), adaptive natural density partitioning (AdNDP) and ultraviolet visible absorption spectrum (UV-Vis) indicate that, the HfSn₁₆ with high symmetry of T_d exhibits thermochemical stability and optoelectronic properties, which is utilized potentially as zero-dimensional unit of self-assembling fluorescent nanomaterials.

Keywords: HfSn(16); Infrared and Raman spectra; Simulated photoelectron spectra; Structural growth behavior; UV–Vis absorption spectrum.