This paper was a pure computational chemistry project studying the photoexcited state of a common conjugated polymer used in organic photovoltaics. It was published in the Journal of Physical Chemistry Letters, DOI: 10.1021/acs.jpclett.7b01053.
This was one of those “why hasn’t anyone done this yet?” projects which Tak gave to one of his honours students, Ras Roseli. She did a great job on the computational work, which I can claim no credit for! I provided the small amount of experimental data and wrote up the manuscript with Tak.
While I think this is a great piece of work for a (technically undergraduate) student, the field of computational chemistry moves fast. If you’re looking to replicate the techniques in this work then I’d recommend looking at some of the newer hybrid density functionals. For example, ωB97X-D, or the even newer ωB2PLYP developed by the Goerigk group.
Fun fact: There’s a spelling error on the first page which is entirely my fault. See if you can find it.
This was a purely computation project based around a quantum mechanical model of molecular spin interactions in the presence of magnetic fields, for the purpose of predicting efficiency of triplet-triplet annihilation upconversion and singlet fission. This was published in the Journal of Physical Chemistry C, DOI: acs.jpcc.6b04934.
It was written in the form of a Comment on a previously published paper. The reason for this was we wanted to use the spin-Hamiltonian method as part of a chapter in my PhD thesis, however the current state of the literature was, frankly, quite obviously wrong. Hence, we took a six month detour to first work on correcting the currently accepted literature reference on the molecular spin-Hamiltonian.
It actually felt kind of bad publishing this, since the Bardeen group is well known and respected. However, it’s science, and if it’s wrong, it’s wrong… right? Funnily enough, after this correction was published, Bardeen contacted David to say “no hard feelings”, which was nice. A few weeks later they published this article. My guess is they had been sitting on that experimental data but since it didn’t match their (wrong) calculations, they didn’t want to publish it. Once the model was corrected, their experimental results actually made sense!
There’s another funny story about this paper. We got sent someone’s manuscript for review which was almost a complete copy of this work. Except they made many of the same mistakes as in the original paper and were claiming we were actually wrong. What made it really funny was they had directly copied passages of text from our article and figure captions. Yes, that paper did eventually get published, and still has some of the original mistakes in it.
This project was primarily computational, involving the development of a hybrid classical and quantum method. It was published in the Journal of Physical Chemistry C, DOI: 10.1021/acs.jpcc.5b00705.
The morphology dependence of exciton transport in the widely used conjugated polymer poly(3-hexylthiophene) (P3HT) is elucidated by combining an accurate mesoscale coarse-grained molecular dynamics simulation model of P3HT structure with a Frenkel–Holstein exciton model. This model provides a more realistic representation than previously achieved of the molecular-level details of exciton transport on large length scales relevant to electronic applications. One hundred 300-monomer regioregular P3HT chains are simulated at room temperature for microseconds in two implicit solvents of differing solvent quality in which the polymer chains adopt contrasting morphologies: nanofiber-like aggregates or well-separated extended conformations. The model gives reasonable quantitative agreement with steady-state absorption and fluorescence and time-resolved fluorescence experiments, and provides valuable insight into the mechanism of exciton transport in conjugated polymers. In particular, exciton transfer in nanofiber aggregates is shown to occur mainly through interchain hops from chromophores on the aggregate surface toward the aggregate core, a behavior with important implications for organic electronic applications. Furthermore, the counterbalancing effects of greater orientational order and faster exciton transport in nanofiber aggregates than in extended chains are found to explain the puzzling observation of similar fluorescence anisotropy decay rates in nanofibers and free chains.