TY - JOUR
T1 - Stability of multiply charged anions of lanthanide hexafluorides LnF6/2- and LnF6/3- (Ln = Ce to Lu)
AU - Takeda, Kou
AU - Tsuchiya, Takashi
AU - Nakano, Haruyuki
AU - Taketsugu, Tetsuya
AU - Hirao, Kimihiko
N1 - Funding Information:
The present research was supported in part by the Grant-in-Aid for Scientific Research on Priority Areas ‘Molecular Physical Chemistry’ from the Ministry of Education, Science, Sports and Culture of Japan.
PY - 2001/3/12
Y1 - 2001/3/12
N2 - The kinetic and electronic stability of a series of free LnF6/9--type lanthanide hexafluorides (Ln = Ce to Lu; q = 2, 3) is studied with the relativistic effective core potentials of Cundari and Stevens. In all complexes (LnF6/2- and LnF6/3-), the octahedral or almost octahedral structure is calculated to be stable through normal mode analyses at the unrestricted Hartree-Fock (UHF) and complete active space self-consistent field (CASSCF) levels. The electronic stability of all complexes is investigated using the state-averaged CASSCF and quasidegenerate perturbation theory with multiconfigurational self-consistent field reference functions (MC-QDPT) schemes. The most electronically stable LnF6/9- is LnF6/2- for Ce, Pr, Nd, Pm, Sm, Tb, Dy, Ho, Er, Tm, Yb. These LnF6/2- anions are found to have an energy barrier with respect to the unimolecular decomposition LnF6/2- → LnF6/5- + F- and are predicted to be long-lived species formally existing in a meta-stable state.
AB - The kinetic and electronic stability of a series of free LnF6/9--type lanthanide hexafluorides (Ln = Ce to Lu; q = 2, 3) is studied with the relativistic effective core potentials of Cundari and Stevens. In all complexes (LnF6/2- and LnF6/3-), the octahedral or almost octahedral structure is calculated to be stable through normal mode analyses at the unrestricted Hartree-Fock (UHF) and complete active space self-consistent field (CASSCF) levels. The electronic stability of all complexes is investigated using the state-averaged CASSCF and quasidegenerate perturbation theory with multiconfigurational self-consistent field reference functions (MC-QDPT) schemes. The most electronically stable LnF6/9- is LnF6/2- for Ce, Pr, Nd, Pm, Sm, Tb, Dy, Ho, Er, Tm, Yb. These LnF6/2- anions are found to have an energy barrier with respect to the unimolecular decomposition LnF6/2- → LnF6/5- + F- and are predicted to be long-lived species formally existing in a meta-stable state.
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U2 - 10.1016/S0166-1280(00)00667-9
DO - 10.1016/S0166-1280(00)00667-9
M3 - Article
AN - SCOPUS:0035848430
SN - 2210-271X
VL - 537
SP - 107
EP - 115
JO - Computational and Theoretical Chemistry
JF - Computational and Theoretical Chemistry
IS - 1
ER -