Optical and magnetic properties of antiaromatic porphyrinoids
| Parent link: | Physical Chemistry Chemical Physics Vol. 19, iss. 38.— 2017.— [P. 25979-25988] |
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| 主要作者: | |
| 企業作者: | |
| 其他作者: | , |
| 總結: | Title screen Magnetic and spectroscopic properties of a number of formally antiaromatic carbaporphyrins, carbathiaporphyrins and isophlorins with 4n ? electrons have been investigated at density functional theory and ab initio levels of theory. The calculations show that the paratropic contribution to the magnetically induced ring-current strength susceptibility and the magnetic dipole-transition moment between the ground and the lowest excited state are related. The vertical excitation energy (VEE) of the first excited state decreases with increasing ring-current strength susceptibility, whereas the VEE of the studied higher-lying excited states are almost independent of the size of the ring-current strength susceptibility. Strong antiaromatic porphyrinoids, based on the magnitude of the paratropic ring-current strength susceptibility, have small energy gaps between the highest occupied and lowest unoccupied molecular orbitals and a small VEE of the first excited state. The calculations show that only the lowest S0 > S1 transition contributes signficantly to the magnetically induced ring-current strength susceptibility of the antiaromatic porphyrinoids. The decreasing optical gap combined with a large angular momentum contribution to the magnetic transition moment from the first excited state explains why molecules III–VII are antiaromatic with very strong paratropic ring-current strength susceptibilities. The S0 > S1 transition is a magnetic dipole-allowed electronic transition that is typical for antiaromatic porphyrinoids with 4n ? electrons. Режим доступа: по договору с организацией-держателем ресурса |
| 語言: | 英语 |
| 出版: |
2017
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| 主題: | |
| 在線閱讀: | http://dx.doi.org/10.1039/C7CP05460B |
| 格式: | 電子 Book Chapter |
| KOHA link: | https://koha.lib.tpu.ru/cgi-bin/koha/opac-detail.pl?biblionumber=656154 |
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| 200 | 1 | |a Optical and magnetic properties of antiaromatic porphyrinoids |f R. R. Valiev, H. Fliegl, D. Sundholm | |
| 203 | |a Text |c electronic | ||
| 300 | |a Title screen | ||
| 330 | |a Magnetic and spectroscopic properties of a number of formally antiaromatic carbaporphyrins, carbathiaporphyrins and isophlorins with 4n ? electrons have been investigated at density functional theory and ab initio levels of theory. The calculations show that the paratropic contribution to the magnetically induced ring-current strength susceptibility and the magnetic dipole-transition moment between the ground and the lowest excited state are related. The vertical excitation energy (VEE) of the first excited state decreases with increasing ring-current strength susceptibility, whereas the VEE of the studied higher-lying excited states are almost independent of the size of the ring-current strength susceptibility. Strong antiaromatic porphyrinoids, based on the magnitude of the paratropic ring-current strength susceptibility, have small energy gaps between the highest occupied and lowest unoccupied molecular orbitals and a small VEE of the first excited state. The calculations show that only the lowest S0 > S1 transition contributes signficantly to the magnetically induced ring-current strength susceptibility of the antiaromatic porphyrinoids. The decreasing optical gap combined with a large angular momentum contribution to the magnetic transition moment from the first excited state explains why molecules III–VII are antiaromatic with very strong paratropic ring-current strength susceptibilities. The S0 > S1 transition is a magnetic dipole-allowed electronic transition that is typical for antiaromatic porphyrinoids with 4n ? electrons. | ||
| 333 | |a Режим доступа: по договору с организацией-держателем ресурса | ||
| 461 | |t Physical Chemistry Chemical Physics | ||
| 463 | |t Vol. 19, iss. 38 |v [P. 25979-25988] |d 2017 | ||
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