Spin Orbit Coupling in Orthogonal Charge Transfer States: (TD-)DFT of Pyrene-Dimethylaniline
Shivan Bissesar1, Davita M E van Raamsdonk1, Dáire J Gibbons1
1Molecular Photonics Group, van 't Hoff Institute for Molecular Sciences (HIMS), Universiteit van Amsterdam, Science Park 904, 1098 XH Amsterdam, The Netherlands.
Abstract:
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).
More Related Videos
11:33All-electronic Nanosecond-resolved Scanning Tunneling Microscopy: Facilitating the Investigation of Single Dopant Charge Dynamics
Published on: January 19, 2018
09:00Experimental Methods for Spin- and Angle-Resolved Photoemission Spectroscopy Combined with Polarization-Variable Laser
Published on: June 28, 2018
Related Concept Videos
Spin–Spin Coupling: Three-Bond Coupling (Vicinal Coupling)
The extent of coupling depends on the C‑C bond length, the two H‑C‑C angles, any electron-withdrawing substituents, and the dihedral angle between the...
Spin–Spin Coupling: Two-Bond Coupling (Geminal Coupling)
The central atom need not be NMR-active because its electrons are affected by the electron polarization of the spin-active atoms. However, spin information is transmitted less effectively than in one-bond coupling, and 2J values are usually weaker than 1J values. The energy of...
Spin–Spin Coupling: One-Bond Coupling
¹H NMR: Long-Range Coupling
In alkenes, spin information is communicated via σ–π overlap, as seen in allylic (four-bond) and homoallylic (five-bond) couplings. These coupling interactions are stronger when the σ bond is parallel to the alkene...
Spin–Spin Coupling Constant: Overview
Qualitatively, any spin plus-half nucleus polarizes the spins of its electrons to the minus-half state. Consequently, the paired electron in the hydrogen–carbon bond must...
NMR Spectroscopy: Spin–Spin Coupling
