Исследование спектра ионизации 6,6-диметил-фульвена методами алгебраического диаграммного построения и связанных кластеров

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Электронная структура и спектр ионизации 6,6-диметил-фульвена рассчитаны с использованием метода алгебраического диаграммного построения третьего порядка для одночастичной функции Грина (IP-ADC(3)) и метода уравнений движения для связанных кластеров в приближении модели однократных и двукратных возбуждений (IP-EOM-CCSD). Результаты использованы для интерпретации недавно полученного фотоэлектронного спектра 6,6-диметил-фульвена [M. H. Palmer et. al, Chem. Phys. Lett. 2022, 796, 139558]. Предложен ряд новых отнесений, среди которых наиболее значимым является отнесение ранее неотнесенного плеча третьей фотоэлектронной полосы в районе 10.5 эВ, которое согласно нашим IP-ADC(3)-расчетам, образовано сателлитными переходами, связанными с p-орбиталями фульвенового кольца 2a2 и 2b1. Полученные в работе данные также позволяют полагать, что у метода IP-EOM-CCSD и эквивалентных ему подходов имеются трудности с корректным описанием сателлитных состояний.

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作者简介

А. Трофимов

ФГБОУ ВО Иркутский государственный университет; ФГБУН Иркутский институт химии им. А. Е. Фаворского СО РАН

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Email: abtrof@mail.ru
俄罗斯联邦, 664003 Иркутск; 664033 Иркутск

А. Скитневская

ФГБОУ ВО Иркутский государственный университет

Email: abtrof@mail.ru
俄罗斯联邦, 664003 Иркутск

А. Белоголова

ФГБОУ ВО Иркутский государственный университет; ФГБУН Иркутский институт химии им. А. Е. Фаворского СО РАН

Email: abtrof@mail.ru
俄罗斯联邦, 664003 Иркутск; 664033 Иркутск

Э. Якимова

ФГБОУ ВО Иркутский государственный университет

Email: abtrof@mail.ru
俄罗斯联邦, 664003 Иркутск

Е. Громов

ФГБОУ ВО Иркутский государственный университет

Email: abtrof@mail.ru
俄罗斯联邦, 664003 Иркутск

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2. Fig. 1. Structure of the most stable conformer of 6,6-dimethyl-fulvene.

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3. Fig. 2. 1-1. Upper occupied MOs of 6,6-dimethyl-fulvene (from HOMO to HOMO-13), their symmetries and energies according to calculation data in the HF/cc-pVTZ approximation, as well as qualitative assignments to different types (s and p).

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4. Fig. 2. 1-2. Upper occupied MOs of 6,6-dimethyl-fulvene (from HOMO to HOMO-13), their symmetries and energies according to calculation data in the HF/cc-pVTZ approximation, as well as qualitative assignments to different types (s and p).

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5. Fig. 2. 2-1. Upper occupied MOs of 6,6-dimethyl-fulvene (from HOMO to HOMO-13), their symmetries and energies according to calculation data in the HF/cc-pVTZ approximation, as well as qualitative assignments to different types (s and p).

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6. Fig. 2. 2-2. Upper occupied MOs of 6,6-dimethyl-fulvene (from HOMO to HOMO-13), their symmetries and energies according to calculation data in the HF/cc-pVTZ approximation, as well as qualitative assignments to different types (s and p).

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7. Fig. 2. 3-1. Upper occupied MOs of 6,6-dimethyl-fulvene (from HOMO to HOMO-13), their symmetries and energies according to calculation data in the HF/cc-pVTZ approximation, as well as qualitative assignments to different types (s and p).

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8. Fig. 2. 3-2. Upper occupied MOs of 6,6-dimethyl-fulvene (from HOMO to HOMO-13), their symmetries and energies according to calculation data in the HF/cc-pVTZ approximation, as well as qualitative assignments to different types (s and p).

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9. Fig. 2. 4-1. Upper occupied MOs of 6,6-dimethyl-fulvene (from HOMO to HOMO-13), their symmetries and energies according to calculation data in the HF/cc-pVTZ approximation, as well as qualitative assignments to different types (s and p).

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10. Fig. 2. 4-2. Upper occupied MOs of 6,6-dimethyl-fulvene (from HOMO to HOMO-13), their symmetries and energies according to calculation data in the HF/cc-pVTZ approximation, as well as qualitative assignments to different types (s and p).

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11. Fig. 2. 5-1. Upper occupied MOs of 6,6-dimethyl-fulvene (from HOMO to HOMO-13), their symmetries and energies according to calculation data in the HF/cc-pVTZ approximation, as well as qualitative assignments to different types (s and p).

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12. Fig. 2. 5-2. Upper occupied MOs of 6,6-dimethyl-fulvene (from HOMO to HOMO-13), their symmetries and energies according to calculation data in the HF/cc-pVTZ approximation, as well as qualitative assignments to different types (s and p).

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13. Fig. 2. 6-1. Upper occupied MOs of 6,6-dimethyl-fulvene (from HOMO to HOMO-13), their symmetries and energies according to calculation data in the HF/cc-pVTZ approximation, as well as qualitative assignments to different types (s and p).

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14. Fig. 2. 6-2. Upper occupied MOs of 6,6-dimethyl-fulvene (from HOMO to HOMO-13), their symmetries and energies according to calculation data in the HF/cc-pVTZ approximation, as well as qualitative assignments to different types (s and p).

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15. Fig. 2. 7-1. Upper occupied MOs of 6,6-dimethyl-fulvene (from HOMO to HOMO-13), their symmetries and energies according to calculation data in the HF/cc-pVTZ approximation, as well as qualitative assignments to different types (s and p).

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16. Fig. 2. 7-2. Upper occupied MOs of 6,6-dimethyl-fulvene (from HOMO to HOMO-13), their symmetries and energies according to calculation data in the HF/cc-pVTZ approximation, as well as qualitative assignments to different types (s and p).

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17. Fig. 3. Theoretical (IP-ADC(3)/cc-pVTZ), calculated in this work, and experimental, from work [8], ionization spectra of 6,6-dimethyl-fulvene. The theoretical spectrum is shifted by –0.30 eV relative to the experimental one; vertical transitions, which can be considered as the main lines (with intensities P ≥ 0.6), are shown in blue; transitions corresponding to satellite lines (P < 0.6) are shown in red.

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18. Fig. 4. Theoretical (IP-EOM-CCSD/cc-pVTZ), calculated in this work, and experimental, from work [8], ionization spectra of 6,6-dimethyl-fulvene. The theoretical spectrum is shifted by –0.2 eV relative to the experimental one; vertical transitions, which can be considered as the main lines (with intensities P ≥ 0.6), are shown in blue, and transitions corresponding to satellite lines (P < 0.6) are shown in red.

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