The ground and first excited states of HoS studied by four-component relativistic KR-MCSCF and KRCI
| العنوان: | The ground and first excited states of HoS studied by four-component relativistic KR-MCSCF and KRCI |
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| المؤلفون: | Hiroshi Tatewaki, Shigeyoshi Yamamoto |
| المصدر: | Theoretical Chemistry Accounts. 139 |
| بيانات النشر: | Springer Science and Business Media LLC, 2020. |
| سنة النشر: | 2020 |
| مصطلحات موضوعية: | Physics, 010304 chemical physics, Ionic bonding, Formal charge, Electron, Configuration interaction, 010402 general chemistry, 01 natural sciences, 0104 chemical sciences, Ion, Excited state, 0103 physical sciences, Physical and Theoretical Chemistry, Atomic physics, Ground state, Configuration state function |
| الوصف: | 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. |
| تدمد: | 1432-2234 1432-881X |
| DOI: | 10.1007/s00214-020-2586-z |
| URL الوصول: | https://explore.openaire.eu/search/publication?articleId=doi_________::e2d7fa98d33967f7d590a9ad3d2ecbbd https://doi.org/10.1007/s00214-020-2586-z |
| Rights: | CLOSED |
| رقم الانضمام: | edsair.doi...........e2d7fa98d33967f7d590a9ad3d2ecbbd |
| قاعدة البيانات: | OpenAIRE |
| تدمد: | 14322234 1432881X |
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| DOI: | 10.1007/s00214-020-2586-z |