TY - JOUR

T1 - Quantum chemical modeling of electron-deficient hollow TlkPb12–k and TlkBi20–k shells and related endohedral complexes (k = 1; 2)

AU - Семенов, Сергей Георгиевич

AU - Бедрина, Марина Евгеньевна

AU - Клемешев, Владимир Алексеевич

AU - Титов, Анатолий Владимирович

N1 - Publisher Copyright: © 2022 Wiley Periodicals LLC.

PY - 2022/12/3

Y1 - 2022/12/3

N2 - The equilibrium structural parameters, symmetry groups, and dipole moments of the free hollow electron-deficient TlBi 19, Tl 2Bi 18, p-, m-, o-Tl 2Pb 10 shells and the endohedral (He, Ne)@Tl 2Pb 10, (Y, La, Lu, Tl, Bi, Ce)@TlPb 11, Tl@(Y, La, Lu) Pb 11, Sr@TlBi 19, Tl@SrBi 19, Yb@TlBi 19, Tl@YbBi 19, [Y@TlBi 19] +, [Lu@TlBi 19] +, Sr@Tl 2Bi 18, and Yb@Tl 2Bi 18 complexes are predicted by using DFT (U)PBE0 hybrid method. The isomerization of (Sr, Yb)@Tl kBi 20–k into Tl@(Sr, Yb) Tl k–1Bi 20–k is endothermic. The isodesmic substitution of an endo-atom in the Tl@TlPb 11 cluster for a rare-earth atom is exothermic. The hollow Tl kBi 20–k (Sr, Yb) complexes with Tl in the shell and with Sr or Yb exo-atom are impossible. The endo-atoms plunge in hollow TlPb 11 and hollow TlBi 19 shells without delay on its surface. The (C 5v)-TlPb 11 and (C 3v)-TlBi 19 shells are stabilized by an endo-atom X with oxidation number Ξ X = +3 and +2, respectively. No one cerium IV oxidation state has been predicted. The integer number Ξ X is presented as a function of the populations of one-electron states in the shell surrounding the endo-atom X. Each Pb or Bi atom in the electron-deficient clusters retains an entirely localized lone electron pair. The change in the IR spectrum when a metal atom is embedded into its cavity indicates a strong interaction between the components of the endohedral complex. Structural aspects of the β-decay of a radioactive endo-atom in the cavity of a metal cluster are discussed.

AB - The equilibrium structural parameters, symmetry groups, and dipole moments of the free hollow electron-deficient TlBi 19, Tl 2Bi 18, p-, m-, o-Tl 2Pb 10 shells and the endohedral (He, Ne)@Tl 2Pb 10, (Y, La, Lu, Tl, Bi, Ce)@TlPb 11, Tl@(Y, La, Lu) Pb 11, Sr@TlBi 19, Tl@SrBi 19, Yb@TlBi 19, Tl@YbBi 19, [Y@TlBi 19] +, [Lu@TlBi 19] +, Sr@Tl 2Bi 18, and Yb@Tl 2Bi 18 complexes are predicted by using DFT (U)PBE0 hybrid method. The isomerization of (Sr, Yb)@Tl kBi 20–k into Tl@(Sr, Yb) Tl k–1Bi 20–k is endothermic. The isodesmic substitution of an endo-atom in the Tl@TlPb 11 cluster for a rare-earth atom is exothermic. The hollow Tl kBi 20–k (Sr, Yb) complexes with Tl in the shell and with Sr or Yb exo-atom are impossible. The endo-atoms plunge in hollow TlPb 11 and hollow TlBi 19 shells without delay on its surface. The (C 5v)-TlPb 11 and (C 3v)-TlBi 19 shells are stabilized by an endo-atom X with oxidation number Ξ X = +3 and +2, respectively. No one cerium IV oxidation state has been predicted. The integer number Ξ X is presented as a function of the populations of one-electron states in the shell surrounding the endo-atom X. Each Pb or Bi atom in the electron-deficient clusters retains an entirely localized lone electron pair. The change in the IR spectrum when a metal atom is embedded into its cavity indicates a strong interaction between the components of the endohedral complex. Structural aspects of the β-decay of a radioactive endo-atom in the cavity of a metal cluster are discussed.

KW - inorganic cluster

KW - localized spinor

KW - lone electron pair

KW - oxidation number

KW - structure

UR - http://www.scopus.com/inward/record.url?scp=85143527814&partnerID=8YFLogxK

UR - https://www.mendeley.com/catalogue/5d781b53-8007-3e24-afb8-eddf05e0ba90/

U2 - 10.1002/qua.27046

DO - 10.1002/qua.27046

M3 - Article

JO - International Journal of Quantum Chemistry

JF - International Journal of Quantum Chemistry

SN - 0020-7608

M1 - e27046

ER -