Revisiting the structural and electronic properties of neutral, mono‐ and di‐anionic titanium‐doped silicon clusters TiSin0/−/2− (n = 6‐16). Issue 18 (20th May 2019)

• Record Type: Journal Article
• Authors: Dong, Caixia; Han, Limin; Yang, Jucai; Cheng, Lin
• Is Part Of: International journal of quantum chemistry. Volume 119:Issue 18(2019)
• Page Start: n/a
• Page End: n/a
• Publication Date: 2019-05-20
• Subjects: adiabatic electron affinity -- relative stability -- simulated photoelectron spectroscopy -- structural growth pattern of Ti‐doped silicon clusters -- vertical detachment energy; Quantum chemistry -- Periodicals; 541.28
• DOI: 10.1002/qua.25978
• Languages: English
• ISSNs: 0020-7608

Abstract

Abstract: The systematic structures search for neutral and Zintl anionic Ti‐doped silicon clusters TiSi n 0/−/2− ( n = 6‐16) have been carried out using the ABCluster global search technique combined with a double‐hybrid density functional method. Based on the predicted energies, adiabatic electron affinities, vertical detachment energies and the consistency between simulated and experimental photoelectron spectroscopy, the true global minimum structures are confirmed. The results show that structural growth pattern of neutral TiSi n clusters is from linked structures ( n = 10‐12) to encapsulated configurations ( n = 13‐16). In contrast, the evolution pattern of Zintl anionic TiSi n −/2− clusters begins with the pentagonal bipyramid structure ( n = 6). As the Si atoms increase, these Si atoms attach to the surface adjacent to Ti atom, and gradually surround Ti atom. Eventually, the encapsulated structure is formed when n = 12. Moreover, two extra electrons not only perfect the structure of TiSi12 but also improve its chemical and thermodynamic stability. Abstract : Unbiased global search methodology, combined with first‐principles calculations, is employed to systematically study the ground state structures and evolution patterns of neutral and Zintl anionic TiSin 0/−/2− ( n = 6‐16). The results show that structural growth pattern of neutral clusters transition from linked structures ( n = 10‐12) to encapsulated configurations ( n = 13‐16). In contrast, the evolution pattern of Zintl anionic TiSin −/2− clusters begins with a pentagonal bipyramid structure at n = 6, and grows to an encapsulated configuration at n = 12.