Optical Spectra of Oligofurans: A Theoretical Approach to the Transition Energies, Reorganization Energies, and the Vibronic Activity
There is experimental evidence of high vibronic activity that accompanies the allowed transition between the ground state and the lowest electronic singlet excited state of oligofurans that contain two, three, and four furan rings. The absorption and emission spectra of the three lowest oligofurans...
| Main Authors: | , , |
|---|---|
| Format: | Article |
| Language: | English |
| Published: |
MDPI AG
2021-11-01
|
| Series: | Molecules |
| Subjects: | |
| Online Access: | https://www.mdpi.com/1420-3049/26/23/7163 |
| _version_ | 1797507351548264448 |
|---|---|
| author | Karolina Filipowska Marek T. Pawlikowski Marcin Andrzejak |
| author_facet | Karolina Filipowska Marek T. Pawlikowski Marcin Andrzejak |
| author_sort | Karolina Filipowska |
| collection | DOAJ |
| description | There is experimental evidence of high vibronic activity that accompanies the allowed transition between the ground state and the lowest electronic singlet excited state of oligofurans that contain two, three, and four furan rings. The absorption and emission spectra of the three lowest oligofurans measured at liquid nitrogen temperature show distinct fine structures that are reproduced using the projection-based model of vibronic coupling (with Dushinsky rotation included) parameterized utilizing either Density Functional Theory (DFT, with several different exchange-correlation functionals) or ab initio (CC2) quantum chemistry calculations. Using as a reference the experimental data concerning the electronic absorption and fluorescence for the eight lowest oligofurans, we first analyzed the performance of the exchange-correlation functionals for the electronic transition energies and the reorganization energies. Subsequently, we used the best functionals alongside with the CC2 method to explore how the reorganization energies are distributed among the totally symmetric vibrations, identify the normal modes that dominate in the fine structures present in the absorption and emission bands, and trace their evolution with the increasing number of rings in the oligofuran series. Confrontation of the simulated spectra with the experiment allows for the verification of the performance of the selected DFT functionals and the CC2 method. |
| first_indexed | 2024-03-10T04:48:18Z |
| format | Article |
| id | doaj.art-5aea8f6ad44745cb82991bf7c8055a8c |
| institution | Directory Open Access Journal |
| issn | 1420-3049 |
| language | English |
| last_indexed | 2024-03-10T04:48:18Z |
| publishDate | 2021-11-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Molecules |
| spelling | doaj.art-5aea8f6ad44745cb82991bf7c8055a8c2023-11-23T02:48:22ZengMDPI AGMolecules1420-30492021-11-012623716310.3390/molecules26237163Optical Spectra of Oligofurans: A Theoretical Approach to the Transition Energies, Reorganization Energies, and the Vibronic ActivityKarolina Filipowska0Marek T. Pawlikowski1Marcin Andrzejak2K. Gumiński Department of Theoretical Chemistry, Jagiellonian University, ul. Gronostajowa 2, 30-387 Kraków, PolandK. Gumiński Department of Theoretical Chemistry, Jagiellonian University, ul. Gronostajowa 2, 30-387 Kraków, PolandK. Gumiński Department of Theoretical Chemistry, Jagiellonian University, ul. Gronostajowa 2, 30-387 Kraków, PolandThere is experimental evidence of high vibronic activity that accompanies the allowed transition between the ground state and the lowest electronic singlet excited state of oligofurans that contain two, three, and four furan rings. The absorption and emission spectra of the three lowest oligofurans measured at liquid nitrogen temperature show distinct fine structures that are reproduced using the projection-based model of vibronic coupling (with Dushinsky rotation included) parameterized utilizing either Density Functional Theory (DFT, with several different exchange-correlation functionals) or ab initio (CC2) quantum chemistry calculations. Using as a reference the experimental data concerning the electronic absorption and fluorescence for the eight lowest oligofurans, we first analyzed the performance of the exchange-correlation functionals for the electronic transition energies and the reorganization energies. Subsequently, we used the best functionals alongside with the CC2 method to explore how the reorganization energies are distributed among the totally symmetric vibrations, identify the normal modes that dominate in the fine structures present in the absorption and emission bands, and trace their evolution with the increasing number of rings in the oligofuran series. Confrontation of the simulated spectra with the experiment allows for the verification of the performance of the selected DFT functionals and the CC2 method.https://www.mdpi.com/1420-3049/26/23/7163time-dependent DFT (TDDFT)CC2ultraviolet and visible range (UV/VIS) spectravibronic couplinghuang-rhys (HR) factors |
| spellingShingle | Karolina Filipowska Marek T. Pawlikowski Marcin Andrzejak Optical Spectra of Oligofurans: A Theoretical Approach to the Transition Energies, Reorganization Energies, and the Vibronic Activity Molecules time-dependent DFT (TDDFT) CC2 ultraviolet and visible range (UV/VIS) spectra vibronic coupling huang-rhys (HR) factors |
| title | Optical Spectra of Oligofurans: A Theoretical Approach to the Transition Energies, Reorganization Energies, and the Vibronic Activity |
| title_full | Optical Spectra of Oligofurans: A Theoretical Approach to the Transition Energies, Reorganization Energies, and the Vibronic Activity |
| title_fullStr | Optical Spectra of Oligofurans: A Theoretical Approach to the Transition Energies, Reorganization Energies, and the Vibronic Activity |
| title_full_unstemmed | Optical Spectra of Oligofurans: A Theoretical Approach to the Transition Energies, Reorganization Energies, and the Vibronic Activity |
| title_short | Optical Spectra of Oligofurans: A Theoretical Approach to the Transition Energies, Reorganization Energies, and the Vibronic Activity |
| title_sort | optical spectra of oligofurans a theoretical approach to the transition energies reorganization energies and the vibronic activity |
| topic | time-dependent DFT (TDDFT) CC2 ultraviolet and visible range (UV/VIS) spectra vibronic coupling huang-rhys (HR) factors |
| url | https://www.mdpi.com/1420-3049/26/23/7163 |
| work_keys_str_mv | AT karolinafilipowska opticalspectraofoligofuransatheoreticalapproachtothetransitionenergiesreorganizationenergiesandthevibronicactivity AT marektpawlikowski opticalspectraofoligofuransatheoreticalapproachtothetransitionenergiesreorganizationenergiesandthevibronicactivity AT marcinandrzejak opticalspectraofoligofuransatheoreticalapproachtothetransitionenergiesreorganizationenergiesandthevibronicactivity |