Koopmans' Theorem and Selection Rules for One-Electron Ionization Processes in Orbitally Degenerate Systems Научная публикация
| Журнал |
Journal of Chemical Physics
ISSN: 0021-9606 , E-ISSN: 1089-7690 |
||
|---|---|---|---|
| Вых. Данные | Год: 2022, Том: 157, Номер: 17, Номер статьи : 174103, Страниц : 14 DOI: 10.1063/5.0110124 | ||
| Ключевые слова | Koopmans' theorem; Photoelectron spectroscopy; Selection rule; Restricted open-shell Hartree-Fock | ||
| Авторы |
|
||
| Организации |
|
Информация о финансировании (1)
| 1 | Министерство науки и высшего образования Российской Федерации (с 15 мая 2018) | 0239-2021-0009 |
Реферат:
One-electron ionization processes X→Xi+ in orbitally degenerate systems, such as atoms with the open-shell configuration pN, can be divided into two groups. The first group involves those processes which are allowed in photoelectron spectra. The processes of this group in atoms obey the familiar selection rules (SRs) formulated within the Russell-Saunders L,S coupling. All other ionization processes, for which SRs are not obeyed, belong to the second group. Here we analyze the validity of Koopmans' theorem (KT) for processes of the second group forbidden by SRs. We show that the general formulation of KT in the Hartree-Fock method [Plakhutin, J.Chem.Phys. 148, 094101 (2018)] is implicitly based on the assumption that a X→Xi+ process is allowed by SRs, and this presents a limitation of KT. To overcome the latter, we prove that the variational condition underlying KT gives different results for SR-allowed and SR-forbidden processes. For the former processes, this condition gives the familiar KT relationship Ii = -εi , while for SR-forbidden processes the respective relationship between Ii and εi takes a more complex form. The practical applicability of the present extension of KT is verified by applying it to the totality of ionization processes in the valence 2s and 2p shells of atoms C, N, and O in their ground and excited states, that involves in all 29 SR-allowed and 34 SR-forbidden processes. For all of these processes, we compare KT estimates of ionization energies (IEs) with the relevant experimental data. For completeness, we also present ΔSCF estimates of IEs.
Библиографическая ссылка:
Plakhutin B.N.
Koopmans' Theorem and Selection Rules for One-Electron Ionization Processes in Orbitally Degenerate Systems
Journal of Chemical Physics. 2022. V.157. N17. 174103 :1-14. DOI: 10.1063/5.0110124 WOS Scopus РИНЦ CAPlus PMID OpenAlex
Koopmans' Theorem and Selection Rules for One-Electron Ionization Processes in Orbitally Degenerate Systems
Journal of Chemical Physics. 2022. V.157. N17. 174103 :1-14. DOI: 10.1063/5.0110124 WOS Scopus РИНЦ CAPlus PMID OpenAlex
Даты:
| Поступила в редакцию: | 15 июл. 2022 г. |
| Принята к публикации: | 3 окт. 2022 г. |
| Опубликована online: | 4 окт. 2022 г. |
| Опубликована в печати: | 1 нояб. 2022 г. |
Идентификаторы БД:
| Web of science: | WOS:000884800300005 |
| Scopus: | 2-s2.0-85141512199 |
| РИНЦ: | 50518947 |
| Chemical Abstracts: | 2022:2811149 |
| PMID (PubMed): | 36347678 |
| OpenAlex: | W4300979852 |
Цитирование в БД:
| БД | Цитирований |
|---|---|
| РИНЦ | 1 |