| Abstrakt: |
Pulsed laser ablation of a HgS(s) precursor shows the formation of small cluster ions, (HgS)n=2–4+, together with HgSn=1–8± and [(HgS)n + Sm]±. The computed structure, atomization energy, and HOMO–LUMO gap energy values of the lowest energy ring singlet show stable (HgS)n=2–8. However, the computed bond conductance of the Hg–Hg bond in (HgS)n shows a high value for (HgS)n=2–4 (ξ = 1.072–0.122), whereas it is low for (HgS)n=5–8 (ξ = 0.039–0.006) and decreases significantly as the ring expands, indicating that (HgS)n≥5 is unstable. It evidences that the weak chemical bonding between Hg2+–Hg2+ closed shell (5d10–5d10) electrons plays a significant role in the stability of ring (HgS)n=2–4. Thus, it validates the experimental observation of stable cluster ions up to (HgS)4+. In contrast, the low energy chain triplet (HgS)n=2–8 shows a progressive increase in stability and bond conductance with chain length, indicating sustained mercurophilic interactions in long chain clusters like its crystal structure. Furthermore, the lowest/low energy isomers of HgSn=1–8 have been computed for their energetics, HOMO–LUMO gaps, and electron affinity using DFT-B3LYP/PBE0 methods. [ABSTRACT FROM AUTHOR] |
