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- Title
The ground and first excited states of HoS studied by four-component relativistic KR-MCSCF and KRCI.
- Authors
Yamamoto, Shigeyoshi; Tatewaki, Hiroshi
- Abstract
The X18.5 ground state and the W17.5 first excited state of the HoS molecule are studied by the four-component Kramers-restricted multiconfiguration self-consistent field (KR-MCSCF) method, with an active space of (4f, 6s)11, and then by the Kramers-restricted configuration interaction method with 27 electrons in Ho(5s), (5p), (4f), (6s), S(3s), and S(3p) correlated. For the X18.5 state, Re, ωe, ΔG1/2, and D0 are calculated as 4.310 au, 477.385 cm−1, 477.72 cm−1, and 3.775 eV, respectively. The values of Re and ΔG1/2 agree well with the observed values of 4.301 au and 463.8811 cm−1, respectively. The dominant configuration state function (CSF) is |(4f5/2)6 (4f7/2,7/2)1 (4f7/2,5/2)1 (4f7/2,3/2)1 (4f7/2,1/2)1 (6s1/2,1/2)1|. This corresponds to the formal charge of Ho2+(5I8)S2−, representing ionic bonding where two electrons, one from [6s] and the other from [4f], are moved from Ho to S. In the doubly occupied S(3p) KR-MCSCF molecular spinors, hybridizations exist between S[3p] atomic spinors and Ho polarization functions [5d*] through which electrons are moved from S to Ho, resulting in covalent bonding. Consequently, ionic bonding is mixed with covalent bonding and 11 electrons of (4f, 6s) move outside the Ho13+([Xe])S2− ion core. The gross atomic charge of Ho is + 0.77 at the CI level. The excitation energy to the W17.5 state is calculated as 0.027 eV, close to the experimental value of 0.031 eV.
- Subjects
EXCITED states; IONIC bonds; ATOMIC charges; COVALENT bonds
- Publication
Theoretical Chemistry Accounts: Theory, Computation, & Modeling, 2020, Vol 139, Issue 3, p1
- ISSN
1432-881X
- Publication type
Article
- DOI
10.1007/s00214-020-2586-z