Global Minimum Search and Bonding Analysis of Tl₂H_x and Tl₃H_y (x=0–6; y=0–5) Series

Abstract

A remarkable distinction between boron and carbon hydrides lies in their extremely different bonding patterns and chemical reactivity, resulting in diverse areas of application. Particularly, carbon, characterized by classical two‐center – two‐electron bonds, gives rise to organic chemistry. In contrast, boron forms numerous exotic and non‐intuitive compounds collectively called non‐classical structures. It is reasonable to anticipate that other elements of Group 13 exhibit their own unusual bonding patterns; however, our knowledge of the hydride chemistry for other elements in Group 13 is much more limited, especially for the heaviest stable element, thallium. In this work, we performed a conformational analysis of Tl2Hx and Tl3Hy (x=0–6, y=0–5) series via Coalescence Kick global minimum search algorithm, DFT, and ab initio quantum chemistry methods; we investigated the bonding pattern using the AdNDP algorithm, thermodynamic stability, and stability toward electron detachment. All found global minimum structures are classified as non‐classical structures featuring at least one multi‐center bond.

Exploring the Tl 2H 2 potential energy surface: A comparative analysis with group 13 systems and experiment

“…Pozdeev et al investigated the global minima of TlH and TlH to better understand the unusual bonding patterns that occur in group 13 elements 27 . Included in their supplementary information is a discussion on spin‐orbit coupling (SOC).…”

“…The trans structure was not mentioned for BH and did not exist as a minimum at the Hartree–Fock level for TlH. Recently, Pozdeev et al investigated the global minima of TlH and TlH () 27 . In their study, Pozdeev and coworkers report that the dibridged isomer is the global minimum along the TlH potential energy surface.…”

Bismuth Infrared Star: Being at a Glance

“…AdNDP is effectively used to decipher the chemical bonding pattern of molecules, [24,25] solid materials, [28,29] and clusters, which is the most essential for the current work; more specifically, it was applied for describing and interpreting structure properties of Boron clusters, [30][31][32][33] Aluminum clusters, [34][35] Tin clusters, [36][37] Germanium [38][39][40] and many others. [41][42][43][44][45][46][47] This makes the approach adequate for bonding analysis of bismuth polycation clusters.…”

“…This method is capable of providing not only Lewis's bonding elements (1c–2e lone pairs and 2c–2e “classical” bonds) but also a non‐classic multi‐center representation of delocalized bonds (nc–2e bonds, where n≥3), which allows to introduce the concepts of aromaticity naturally. AdNDP is effectively used to decipher the chemical bonding pattern of molecules, [24,25] solid materials, [28,29] and clusters, which is the most essential for the current work; more specifically, it was applied for describing and interpreting structure properties of Boron clusters, [30–33] Aluminum clusters, [34–35] Tin clusters, [36–37] Germanium [38–40] and many others [41–47] . This makes the approach adequate for bonding analysis of bismuth polycation clusters.…”