Spin Orbit Coupling in Orthogonal Charge Transfer States: (TD-)DFT of Pyrene—Dimethylaniline
The conformational dependence of the matrix element for spin–orbit coupling and of the electronic coupling for charge separation are determined for an electron donor–acceptor system containing a pyrene acceptor and a dimethylaniline donor. Different kinetic and energetic aspects that play a role in...
| Main Authors: | , , , |
|---|---|
| Format: | Article |
| Language: | English |
| Published: |
MDPI AG
2022-01-01
|
| Series: | Molecules |
| Subjects: | |
| Online Access: | https://www.mdpi.com/1420-3049/27/3/891 |
| _version_ | 1797486074965000192 |
|---|---|
| author | Shivan Bissesar Davita M. E. van Raamsdonk Dáire J. Gibbons René M. Williams |
| author_facet | Shivan Bissesar Davita M. E. van Raamsdonk Dáire J. Gibbons René M. Williams |
| author_sort | Shivan Bissesar |
| collection | DOAJ |
| description | The conformational dependence of the matrix element for spin–orbit coupling and of the electronic coupling for charge separation are determined for an electron donor–acceptor system containing a pyrene acceptor and a dimethylaniline donor. Different kinetic and energetic aspects that play a role in the spin–orbit charge transfer intersystem crossing (SOCT-ISC) mechanism are discussed. This includes parameters related to initial charge separation and the charge recombination pathways using the Classical Marcus Theory of electron transfer. The spin–orbit coupling, which plays a significant role in charge recombination to the triplet state, can be probed by (TD)-DFT, using the latter as a tool to understand and predict the SOCT-ISC mechanism. The matrix elements for spin–orbit coupling for acetone and 4-thio-thymine are used for benchmarking. (Time Dependent-) Density Functional Theory (DFT and TD-DFT) calculations are applied using the quantum chemical program Amsterdam Density Functional (ADF). |
| first_indexed | 2024-03-09T23:28:00Z |
| format | Article |
| id | doaj.art-2583ac99016240569b125d8934cb8e8c |
| institution | Directory Open Access Journal |
| issn | 1420-3049 |
| language | English |
| last_indexed | 2024-03-09T23:28:00Z |
| publishDate | 2022-01-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Molecules |
| spelling | doaj.art-2583ac99016240569b125d8934cb8e8c2023-11-23T17:14:17ZengMDPI AGMolecules1420-30492022-01-0127389110.3390/molecules27030891Spin Orbit Coupling in Orthogonal Charge Transfer States: (TD-)DFT of Pyrene—DimethylanilineShivan Bissesar0Davita M. E. van Raamsdonk1Dáire J. Gibbons2René M. Williams3Molecular Photonics Group, van ’t Hoff Institute for Molecular Sciences (HIMS), Universiteit van Amsterdam, Science Park 904, 1098 XH Amsterdam, The NetherlandsMolecular Photonics Group, van ’t Hoff Institute for Molecular Sciences (HIMS), Universiteit van Amsterdam, Science Park 904, 1098 XH Amsterdam, The NetherlandsMolecular Photonics Group, van ’t Hoff Institute for Molecular Sciences (HIMS), Universiteit van Amsterdam, Science Park 904, 1098 XH Amsterdam, The NetherlandsMolecular Photonics Group, van ’t Hoff Institute for Molecular Sciences (HIMS), Universiteit van Amsterdam, Science Park 904, 1098 XH Amsterdam, The NetherlandsThe conformational dependence of the matrix element for spin–orbit coupling and of the electronic coupling for charge separation are determined for an electron donor–acceptor system containing a pyrene acceptor and a dimethylaniline donor. Different kinetic and energetic aspects that play a role in the spin–orbit charge transfer intersystem crossing (SOCT-ISC) mechanism are discussed. This includes parameters related to initial charge separation and the charge recombination pathways using the Classical Marcus Theory of electron transfer. The spin–orbit coupling, which plays a significant role in charge recombination to the triplet state, can be probed by (TD)-DFT, using the latter as a tool to understand and predict the SOCT-ISC mechanism. The matrix elements for spin–orbit coupling for acetone and 4-thio-thymine are used for benchmarking. (Time Dependent-) Density Functional Theory (DFT and TD-DFT) calculations are applied using the quantum chemical program Amsterdam Density Functional (ADF).https://www.mdpi.com/1420-3049/27/3/891triplet formationcharge recombinationcharge separationintersystem crossingSOCT-ISCSOCME |
| spellingShingle | Shivan Bissesar Davita M. E. van Raamsdonk Dáire J. Gibbons René M. Williams Spin Orbit Coupling in Orthogonal Charge Transfer States: (TD-)DFT of Pyrene—Dimethylaniline Molecules triplet formation charge recombination charge separation intersystem crossing SOCT-ISC SOCME |
| title | Spin Orbit Coupling in Orthogonal Charge Transfer States: (TD-)DFT of Pyrene—Dimethylaniline |
| title_full | Spin Orbit Coupling in Orthogonal Charge Transfer States: (TD-)DFT of Pyrene—Dimethylaniline |
| title_fullStr | Spin Orbit Coupling in Orthogonal Charge Transfer States: (TD-)DFT of Pyrene—Dimethylaniline |
| title_full_unstemmed | Spin Orbit Coupling in Orthogonal Charge Transfer States: (TD-)DFT of Pyrene—Dimethylaniline |
| title_short | Spin Orbit Coupling in Orthogonal Charge Transfer States: (TD-)DFT of Pyrene—Dimethylaniline |
| title_sort | spin orbit coupling in orthogonal charge transfer states td dft of pyrene dimethylaniline |
| topic | triplet formation charge recombination charge separation intersystem crossing SOCT-ISC SOCME |
| url | https://www.mdpi.com/1420-3049/27/3/891 |
| work_keys_str_mv | AT shivanbissesar spinorbitcouplinginorthogonalchargetransferstatestddftofpyrenedimethylaniline AT davitamevanraamsdonk spinorbitcouplinginorthogonalchargetransferstatestddftofpyrenedimethylaniline AT dairejgibbons spinorbitcouplinginorthogonalchargetransferstatestddftofpyrenedimethylaniline AT renemwilliams spinorbitcouplinginorthogonalchargetransferstatestddftofpyrenedimethylaniline |